Functionalized Polymers Tread Additive For Improved Winter Tire Performance

ABSTRACT

An elastomeric composition is disclosed. The elastomeric composition includes, per 100 parts by weight of rubber (phr): about 30 to about 70 phr of polybutadiene having a cis- 1,4 linkage content of at least 95%; about 30 to 70 phr of natural rubber or polyisoprene; about 20 to 50 phr of a processing oil; a curative agent; an antioxidant; about 50 to about 80 phr filler; a silane compling agent; and about 5 to about 30 phr of a polymer selected from the group consisting of ethylene-propylene-diene terpolymer, butyl mbber, poly(isobutylene-co- para-methylstyrene) and poly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer. The polymer based on ethylene-propylene-diene terpolymer, butyl rubber, poly(isobutylene-co-para-methylstyrene) and poly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer may be functionalized.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority benefit of USSN 62/949,127, filedDec. 17, 2019, which is incorporated herein by reference. This inventionis related to concurrently filed USSN 62/949,088 entitled“FUNCTIONALIZED POLYMERS TREAD ADDITIVE FOR IMPROVED WET BRAKING ANDROLLING RESISTANCE IN HIGH SILICA SUMMER TIRE,” USNN 62/949,116 entitled“FUNCTIONALIZED POLYMERS TREAD ADDITIVE FOR IMPROVED WET BRAKING ANDROLLING RESISTANCE IN LOW SILICA SUMMER TIRE,” USNN 62/949,186 entitled“FUNCTIONALIZED POLYMERS TREAD ADDITIVE TO IMPROVE TRUCK AND BUS RADIALTIRE PERFORMANCE,” USNN 62/949,136 entitled “FUNCTIONALIZED POLYMERSTREAD ADDITIVE TO IMPROVE TIRE PERFORMANCE FOR ALL-SEASON TREADCONTAINING HIGH POLYBUTADIENE LEVEL,” USNN 62/949,151 entitled“FUNCTIONALIZED POLYMERS TREAD ADDITIVE TO IMPROVE TIRE PERFORMANCE FORIMMISCIBLE ALL-SEASON TREAD” and USNN 62/949,175 entitled“FUNCTIONALIZED POLYMERS TREAD ADDITIVE TO IMPROVE ALL-SEASON TIREPERFORMANCE,” the disclosures of which are incorporated herein byreference.

FIELD OF THE INVENTION

The present invention relates to polymers useful as modifiers for tiretreads.

BACKGROUND OF THE INVENTION

The tire tread compound is an important compound in a tire that dictateswear, traction, and rolling resistance. It is a technical challenge todeliver excellent traction, low rolling resistance while providing goodtread wear. The challenge lies in the trade-off between wet traction androlling resistance/tread wear. Raising the compound glass transitiontemperature (Tg) provides better wet traction but, at the same time,increases the rolling resistance and tread wear. There is still a needto develop a tread compound additive that can provide good wet tractionwithout increasing rolling resistance and tread wear.

Functionalized SBR (styrene butadiene rubber) is one method to improvethis trade-off by improving filler dispersion. NANOPRENE™, sub-micron tomicron sized gels from Lanxess with cross-linked butadiene cores andacrylic shells, is another additive used to increase the wet tractionwithout affecting rolling resistance. However, Nanoprene can onlydeliver limited improvement in wet traction.

Related references include PCT Publications WO2019/199833,WO2019/199835, WO2019/199839 and WO2019/199840.

SUMMARY OF THE INVENTION

Described herein is an elastomeric composition comprising, per 100 partsby weight of rubber (phr): about 30 to about 70 phr of polybutadienehaving a cis-1,4 linkage content of at least 95%; about 30 to 70 phr ofnatural rubber or polyisoprene; about 20 to 50 phr processing oil; acurative agent; an antioxidant; about 50 to about 80 phr filler; asilane coupling agent; and about 5 to about 30 phr of a polymer selectedfrom the group consisting of ethylene-propylene-diene terpolymer, butylrubber, poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 illustrates a ¹H-NMR spectra of partially epoxidized butyl rubberobtained via reactive mixing.

FIG. 2 illustrates a ¹H-NMR spectra of partially epoxidizedethylene-propylene-diene terpolymer obtained by a reactive mixingprocess.

FIG. 3 illustrates a ¹H-NMR spectra of thioacetate functionalizedpoly(isobutylene-co-para-methylstyrene) obtained by a solution process.

FIG. 4 illustrates a ¹H-NMR spectra of thioacetate functionalized butylrubber obtained by a reactive mixing process.

FIG. 5 illustrates a ¹H-NMR spectrum of mercaptobenzothiazolefunctionalized poly(isobutylene-co-para-methylstyrene) obtained by areactive mixing process.

FIG. 6 illustrates a ¹H-NMR spectra of mercaptobenzothiazolefunctionalized butyl rubber obtained by a reactive mixing process.

FIG. 7 illustrates a ¹H-NMR spectra ofpoly(isobutylene-co-para-methylstyrene)-amine ionomer obtained by areactive mixing process.

FIG. 8 illustrates a ¹H-NMR spectra of butyl-amine ionomer obtained by areactive mixing process.

FIG. 9 illustrates a ¹H-NMR spectra of modifiedpoly(isobutylene-co-para-methylstyrene) containing citranellol obtainedby a solution process.

FIG. 10 illustrates a ¹H-NMR spectra ofpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer 1.

FIG. 11 illustrates a ¹H-NMR spectra of ethylene-propylene-dieneterpolymer 1.

DETAILED DESCRIPTION OF THE INVENTION

This invention is directed to the use of polymer additives based onbutyl rubber, ethylene-propylene-diene terpolymer,poly(isobutylene-co-para-methylstyrene) polymer andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer. Thesepolymers, which may be functionalized, are useful in tire treadcompositions.

It is a technical challenge to deliver excellent traction, low rollingresistance while providing good tread wear. The challenge lies in thetrade-off between wet traction and rolling resistance/tread wear. Oneway to improve rolling resistance and wet braking is to incorporate aseries of polyolefin additives based on butyl rubber,ethylene-propylene-diene terpolymer,poly(isobutylene-co-para-methylstyrene) polymer andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer in tiretread compositions.

Development of an immiscible functionalized polyolefin (PO) additiveincreases hysteresis in the wet traction region (0° C.) and lowershysteresis in the rolling resistance region (60° C.) without changingthe overall compound Tg by improving the interface between the polymerdomain and the tread matrix. Without wishing to be bound by any theory,the applicants believe that the addition of the functionalized POprovides a robust interface between the polymer domain and the treadmatrix by concentrating the carbon black and antioxidant in thefunctionalized PO domain to improve abrasion resistance, cure state andUV stability.

In one embodiment, an elastomeric composition comprises, per 100 partsby weight of rubber (phr): about 30 to about 70 phr of polybutadienehaving a cis-1,4 linkage content of at least 95%; about 30 to 70 phr ofnatural rubber or polyisoprene; about 20 to 50 phr processing oil; acurative agent; an antioxidant; about 50 to about 80 phr filler; asilane coupling agent; and about 5 to about 30 phr of a polymer selectedfrom the group consisting of ethylene-propylene-diene terpolymer, butylrubber, poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer.

The butyl copolymer rubbers are prepared by polymerizing (i) C4-C7isoolefins with (ii) C4-C14 conjugated dienes. The butyl copolymerrubbers contain from 85 to 99.5 mol% C4-C7 isoolefins and from 0.5 to 15mol% C4-C14 conjugated dienes. Preferably, the butyl copolymer rubber isButyl 365 (ExxonMobil Chemical). In an embodiment, the butyl copolymerrubbers may be halogenated. Preferably, the halogenated butyl copolymerrubber is Exxon™ bromobutyl rubber or Exxon™ chlorobutyl rubber.

The ethylene-propylene-diene terpolymers are prepared by polymerizing(i) propylene with (ii) at least one of ethylene and C₄-C₂₀ α-olefinsand (iii) one or more dienes such as ethylidene norbornene. In anembodiment, the ethylene-propylene-diene terpolymer may be halogenated.In another embodiment, the ethylene-propylene-diene terpolymer isamorphous ethylene-propylene-diene terpolymer.

The poly(isobutylene-co-para-methylstyrene) polymers (BIMSM) areprepared as described in U.S. Pat. No. 5,162,445. A catalyst solution ofethyl aluminum dichloride in methyl chloride is added to a feed blend ofmethyl chloride, isobutylene and para-methylstyrene in a reactor. Thereactor is quenched by cold methanol, the methyl chloride is flashed offand the BIMSM polymer is washed in methanol. Preferably, thepoly(isobutylene-co-para-methylstyrene) polymer is Exxpro™ NPX 1602(ExxonMobil Chemical). In an embodiment, thepoly(isobutylene-co-para-methylstyrene) polymer may be halogenated.Preferably, the halogenated poly(isobutylene-co-para-methylstyrene)polymer is a brominated poly(isobutylene-co-para-methylstyrene) polymersuch as Exxpro™ 3035, 3433, 3563 or 3745. In an embodiment, thepoly(isobutylene-co-para-methylstyrene) polymer may be functionalized asdescribed in U.S. Pat. No. 5,162,445 or as described herein.

The poly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymers(IB-IP-PMS) are prepared as described in U.S. Pat. No. 6,960,632 or asdescribed herein. Poly(isobutylene-co-para-methylstyrene-co-isoprene)terpolymer is prepared by adding an initiator/co-initiator solution to amixed para-methyl styrene, isoprene, and isobutylene monomer solutionusing standard slurry cationic polymerization techniques. In anembodiment, the poly(isobutylene-co-para-methylstyrene-co-isoprene)terpolymer may be halogenated.

The tire tread composition is an important aspect in a tire thatdictates wear, traction, and rolling resistance. It is a technicalchallenge to deliver excellent traction and low rolling resistance whileproviding good tread wear. The challenge lies in the trade-off betweenwet traction and rolling resistance/tread wear. Typically, raising thecomposition’s glass transition temperature (Tg) would provide good wettraction but, at the same time, increase the rolling resistance andtread wear. The embodiments described herein, on the other hand, providea tread compound additive that can deliver superior wet traction withoutlowering the rolling resistance and tread wear.

The problem has been approached by developing an additive, a polymerthat increases hysteresis in the wet traction region (0° C.) and lowershysteresis in the rolling resistance region (60° C.) without changingthe overall compound Tg. The present embodiments described hereinovercome one or more of these deficiencies.

The tread compositions described herein is suitable for use in wintertires typically used by high-performance vehicles. That is, themechanical properties of the tread compounds indicate that correspondingtires would have enhanced handling (e.g., greater traction and grip) andimproved braking capabilities.

Butyl Copolymer Rubber

The term “butyl rubber” or “butyl rubber copolymer” as used in thespecification means copolymers of C₄ to C₇ isoolefins and C₄ to C₁₄conjugated dienes which comprise about 0.5 to about 15 mol% conjugateddiene and about 85 to 99.5 mol% isoolefin. Illustrative examples of theisoolefins which may be used in the preparation of butyl rubber areisobutylene, 2-methyl-1-propene, 3-methyl-1-butene, 4-methyl-1-penteneand beta-pinene. Illustrative examples of conjugated dienes which may beused in the preparation of butyl rubber are isoprene, butadiene,2,3-dimethyl butadiene, piperylene, 2,5-dimethylhexa-2,4-diene,cyclopentadiene, cyclohexadiene and methylcyclopentadiene. Thepreparation of butyl rubber is described in U.S. Pat. No. 2,356,128 andis further described in an article by R. M. Thomas et al. in Ind. & Eng.Chem., vol. 32, pp. 1283 et seq., Oct., 1940. Butyl rubber generally hasa viscosity average molecular weight between about 100,000 to about1,500,000, preferably about 250,000 to about 800,000 and a Wijs IodineNo. (INOPO) of about 0.5 to 50, preferably 1 to 20 (for a description ofthe INOPO test, see Industrial and Engineering Chemistry, Vol. 17, p.367, 1945).

The term “butyl rubber” also encompasses functionalized butyl rubbercompounds described herein.

The butyl rubber may have a C₄ to C₇ isoolefin(s) amount of from about85 to about 99.5 mol%, or from about 90 to about 99.5 mol% or from about95 to about 99.5 mol% based on the weight of the butyl rubber.

The butyl rubber may have a C₄ to C₁₄ conjugated diene(s) amount of fromabout 0.5 to about 15 mol%, or from about 0.5 to about 10 mol% or fromabout 0.5 to about 5 mol%, based on the weight of the butyl rubber.

An example of a butyl rubber is BUTYL 365 or 365S (butyl,isobutylene-isoprene rubber (IIR), available from ExxonMobil ChemicalCompany). BUTYL 365 or 365S is a copolymer of isobutylene and isoprenewith about 2.3 mole% unsaturation. Other examples are Exxon BUTYL 065 or065S (copolymer of isobutylene and isoprene with about 1.05 mole%unsaturation), Exxon BUTYL 068 (copolymer of isobutylene and isoprenewith about 1.15 mole% unsaturation) and Exxon BUTYL 268 or 268S(copolymer of isobutylene and isoprene with about 1.7 mole%unsaturation).

In an embodiment, the butyl copolymer rubber may be halogenated.Preferably, the halogenated butyl copolymer rubber is brominated poly(isobutylene-co-isoprene). Examples of halogenated butyl copolymerrubbers are Exxon™ bromobutyl rubber or Exxon™ chlorobutyl rubber. Anexample of a halogenated butyl copolymer is Bromobutyl 2222 (ExxonMobilChemical). Another example of a halogenated butyl rubber is Exxon SBB6222 (Exxon Mobil), a brominated star branched butyl rubber.

In one embodiment, the butyl rubber is functionalized with sulfur.

In another embodiment, the butyl rubber is functionalized with sulfurand an activator. In a further embodiment, the activator is zinc oxideor stearic acid. In a further embodiment, the activator is a combinationof zinc oxide and stearic acid.

In another embodiment, the butyl rubber is functionalized with sulfurand a silane coupling agent. In a further embodiment, the silanecoupling agent is bis(3-triethoxysilylpropyl)tetrasulphide (TESPT)(available as Si69^(Ⓡ) from Evonik Industries) and bis[3-(diethoxyoctyloxysilyl)propyl]tetrasulfide (from Shin-Etsu).

In another embodiment, the butyl rubber is functionalized with sulfur,an activator and a silane coupling agent.

In another embodiment, the butyl rubber is functionalized with sulfurand a vulcanizing accelerator. In a further embodiment, the vulcanizingaccelerator is n-tertiarybutyl-2-benzothiazyl sulfenamide (TBBS).

The inventive compositions may include the butyl rubber in an amount offrom 5 phr to 30 phr, or from 5 phr to 25 phr.

Ethylene-Propylene-Diene Terpolymer

The “ethylene-propylene-diene terpolymer” as used herein may be anypolymer comprising propylene and other comonomers. The term “polymer”refers to any carbon-containing compound having repeat units from one ormore different monomers. The term “terpolymer” as used herein refers toa polymer synthesized from three different monomers.

The term “ethylene-propylene-diene terpolymer” also encompassesfunctionalized ethylene-propylene-diene terpolymer compounds describedherein.

Terpolymers, in some embodiments, may be produced (1) by mixing allthree monomers at the same time or (2) by sequential introduction of thedifferent comonomers. The mixing of comonomers may be done in one, two,or possible three different reactors in series and/or in parallel.Preferably the ethylene-propylene-diene terpolymer comprises (i)propylene-derived units, (ii) α-olefin-derived units and (iii)diene-derived units. The ethylene-propylene-diene terpolymer may beprepared by polymerizing (i) propylene with (ii) at least one ofethylene and C₄-C₂₀ α-olefins and (iii) one or more dienes.

The comonomers may be linear or branched. Preferred linear comonomersinclude ethylene or C₄ to C₈ α-olefins, more preferably ethylene,1-butene, 1-hexene, and 1-octene, even more preferably ethylene or1-butene. Preferred branched comonomers include 4-methyl-1-pentene,3-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene. In one or moreembodiments, the comonomers may include styrene.

The dienes may be conjugated or non-conjugated. Preferably, the dienesare non-conjugated. Illustrative dienes may include, but are not limitedto, 5-ethylidene-2-norbornene (ENB); 1,4-hexadiene;5-methylene-2-norbornene (MNB); 1,6-octadiene; 5-methyl-1,4-hexadiene;3,7-dimethyl-1,6-octadiene; 1,3-cyclopentadiene; 1,4-cyclohexadiene;vinyl norbornene (VNB); dicyclopendadiene (DCPD); and combinationsthereof. Preferably, the diene is ENB or VNB. Preferably, theethylene-propylene-diene terpolymer comprises an ENB content of from 0.5wt% to 8 wt% based on the weight of the terpolymer, or from 2 wt% to 6wt%, or from 3 wt% to 5 wt%. More preferably, theethylene-propylene-diene terpolymer comprises an ENB content of from 0.5wt% to 3 wt%.

The ethylene-propylene-diene terpolymer may have a propylene amount offrom 65 wt% to 95 wt%, or from 70 wt% to 95 wt%, or from 75 wt% to 95wt%, or from 80 wt% to 95 wt%, or from 83 wt% to 95 wt%, or from 84 wt%to 95 wt%, or from 84 wt% to 94 wt%, or from 72 wt% to 95 wt%, or from80 wt% to 93 wt%, or from 85 wt% to 89 wt%, based on the weight of thepolymer. The balance of the ethylene-propylene-diene terpolymercomprises at least one of ethylene and C₄-C₂₀ α-olefin and one or moredienes. The α-olefin may be ethylene, butene, hexane, or octene. Whentwo or more α-olefins are present in the polymer, ethylene and at leastone of butene, hexane, or octene are preferred.

Preferably, the ethylene-propylene-diene terpolymer comprises from 2 to30 wt% of C₂ and/or C₄-C₂₀ α-olefins based the weight of theethylene-propylene-diene terpolymer. When two or more of ethylene andC₄-C₂₀ α-olefins are present the combined amounts of these olefins inthe polymer is preferably at least 2 wt% and falling within the rangesdescribed herein. Other preferred ranges of the amount of ethyleneand/or one or more α-olefins include from 2 wt% to 15 wt%, or from 5 wt%to 15 wt%, or from 8 wt% to 15 wt%, or from 8 to 12 wt%, based on theweight of the ethylene-propylene-diene terpolymer.

Preferably, the ethylene-propylene-diene terpolymer comprises anethylene content of from 5 wt% to 25 wt% based on the weight of theterpolymer, or from 8 wt% to 12 wt%.

Preferably, the ethylene-propylene-diene terpolymer comprises a dienecontent of from 1 wt% to 16 wt% based on the weight of the terpolymer,or from 1 wt% to 12 wt%, or 2 wt% to 6 wt%, or from 2 wt% to 6 wt%.

In one embodiment, the ethylene-propylene-diene terpolymer ishalogenated. The ethylene-propylene-diene terpolymer may be halogenatedby methods known in the art or by methods described in U.S. Pat. No.4,051,083.

In one embodiment, the synthesis of the ethylene-propylene-dieneterpolymer utilizes abis((4-triethylsilyl)phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium dimethyl catalyst precursor. However, other metalloceneprecursors with good diene incorporation and MW capabilities could alsobe used. The synthesis of the ethylene-propylene-diene terpolymer alsoutilizes a dimethylanilinium tetrakis(pentafluorophenyl)borate activatorbut dimethylanilinium-tetrakis(heptafluoronaphthyl)borate and othernon-coordinating anion type activators or MAO could also be used.

In a reactor, a copolymer material is produced in the presence ofethylene, propylene, ethylidene norbornene, and a catalyst comprisingthe reaction product of N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate and[cyclopentadienyl(2,7-di-t-butylfluorenyl)di-p-triethylsilanephenylmethane]hafnium dimethyl. The copolymer solution emerging from the reactor isquenched and then devolatilized using conventionally knowndevolatilization methods, such as flashing or liquid phase separation,first by removing the bulk of the isohexane to provide a concentratedsolution, and then by stripping the remainder of the solvent inanhydrous conditions using a devolatilizer so as to end up with a moltenpolymer composition containing less than 0.5 wt% of solvent and othervolatiles. The molten polymer composition was advanced by a screw to apelletizer from which the ethylene-propylene-diene terpolymercomposition pellets are submerged in water and cooled until solid.

The ethylene-propylene-diene terpolymer may have a melt flow rate (MFR,2.16 kg weight at 230° C.), equal to or greater than 0.1 g/10 min asmeasured according to the ASTM D-1238-13. Preferably, the MFR (2.16 kgat 230° C.) is from 0.5 g/10 min to 200 g/10 min, or from 0.5 g/10 minto 100 g/10 min, or from 0.5 g/10 min to 30 g/10 min, or from 0.5 g/10min to 10 g/10 min, or from 0.5 g/10 min to 5 g/10 min, or from 0.5 g/10min to 2 g/10 min, or from 0.1 g/10 min to 15 g/10 min.

The ethylene-propylene-diene terpolymer may have a heat of fusion(H_(f)) determined by the DSC procedure described herein, which isgreater than or equal to 0 Joules per gram (J/g), and is equal to orless than 80 J/g, or equal to or less than 75 J/g, or equal to or lessthan 70 J/g, or equal to or less than 60 J/g, or equal to or less than50 J/g, or equal to or less than 35 J/g. Preferably, the H_(f) is 0 J/g.

The crystallinity of the ethylene-propylene-diene terpolymer may beexpressed in terms of percentage of crystallinity (i.e.,%crystallinity), as determined according to the DSC procedure describedherein. The ethylene-propylene-diene terpolymer may have a %crystallinity of from 0% to 40%. Preferably, the % crystallinity is 0%.The ethylene-propylene-diene terpolymer preferably may have a singlebroad melting transition. However, the ethylene-propylene-dieneterpolymer may show secondary melting peaks adjacent to the principalpeak, but for purposes herein, such secondary melting peaks areconsidered together as a single melting point, with the highest of thesepeaks (relative to baseline as described herein) being considered as themelting point of the ethylene-propylene-diene terpolymer.

The Differential Scanning Calorimetry (DSC) procedure may be used todetermine heat of fusion and melting temperature of theethylene-propylene-diene terpolymer. The method is as follows:approximately 6 mg of material placed in microliter aluminum sample pan.The sample is placed in a Differential Scanning Calorimeter (PerkinElmer Pyris 1 Thermal Analysis System) and is cooled to -80° C. Thesample is heated at 10° C./min to attain a final temperature of 120° C.The sample is cycled twice. The thermal output, recorded as the areaunder the melting peak of the sample, is a measure of the heat of fusionand may be expressed in Joules per gram of polymer and is automaticallycalculated by the Perkin Elmer System. The melting point is recorded asthe temperature of the greatest heat absorption within the range ofmelting of the sample relative to a baseline measurement for theincreasing heat capacity of the polymer as a function of temperature.

The ethylene-propylene-diene terpolymer may be a blend of discreterandom ethylene-propylene-diene terpolymers as long as the polymer blendhas the properties of the ethylene-propylene-diene terpolymer asdescribed herein. The number of ethylene-propylene-diene terpolymers maybe three or less, or two or less. In one or more embodiments, theethylene-propylene-diene terpolymer may include a blend of twoethylene-propylene-diene terpolymers differing in the olefin content,the diene content, or the both.

In one embodiment, the ethylene-propylene-diene terpolymer isfunctionalized with sulfur.

In another embodiment, the ethylene-propylene-diene terpolymer isfunctionalized with sulfur and an activator. In a further embodiment,the activator is zinc oxide or stearic acid. In a further embodiment,the activator is a combination of zinc oxide and stearic acid.

In another embodiment, the ethylene-propylene-diene terpolymer isfunctionalized with sulfur and a silane coupling agent. In a furtherembodiment, the silane coupling agent isbis(3-triethoxysilylpropyl)tetrasulphide (TESPT) (available as Si69Ⓡfrom Evonik Industries) and bis[3-(diethoxyoctyloxysilyl)propyl]tetrasulfide (from Shin-Etsu).

In another embodiment, the ethylene-propylene-diene terpolymer isfunctionalized with sulfur, an activator and a silane coupling agent.

In another embodiment, the ethylene-propylene-diene terpolymer isfunctionalized with sulfur and a vulcanizing accelerator. In a furtherembodiment, the vulcanizing accelerator isn-tertiary-butyl-2-benzothiazyl sulfenamide (TBBS).

The inventive compositions may include the ethylene-propylene-dieneterpolymer in an amount of from 5 phr to 30 phr, or from 5 phr to 25phr, or from 10 phr to 20 phr.

Poly(isobutylene-co-para-methylstyrene)

The term “poly(isobutylene-co-para-methylstyrene)” as used in thespecification means a co-polymer of isobutylene and para-methylstyrene.

The term “poly(isobutylene-co-para-methylstyrene)” also encompassesfunctionalized poly(isobutylene-co-para-methylstyrene) compoundsdescribed herein.

Preferably, the poly(isobutylene-co-para-methylstyrene) polymer isExxpro™ NPX 1602 (ExxonMobil Chemical). In one embodiment, thepoly(isobutylene-co-para-methylstyrene) polymer is halogenated.Brominated poly(isobutylene-co-para-methylstyrene) polymer may beobtained, for example, as Exxpro 3035, 3433, 3565 or 3745, a trademarkof the ExxonMobil Chemical Company. Exxpro 3035, 3433, 3565 and 3745 arebrominated copolymers of isobutylene and paramethylstyrene containingabout 0.47, 0.75, 0.85 and 1.2 mol% benzylic bromine, respectively.

In one embodiment, the poly(isobutylene-co-para-methylstyrene) polymeris functionalized with sulfur.

In another embodiment, the poly(isobutylene-co-para-methylstyrene)polymer is functionalized with sulfur and an activator. In a furtherembodiment, the activator is zinc oxide or stearic acid. In a furtherembodiment, the activator is a combination of zinc oxide and stearicacid.

In another embodiment, the poly(isobutylene-co-para-methylstyrene)polymer is functionalized with sulfur and a silane coupling agent. In afurther embodiment, the silane coupling agent isbis(3-triethoxysilylpropyl)tetrasulphide (TESPT) (available as Si69Ⓡfrom Evonik Industries) and bis[3-(diethoxyoctyloxysilyl)propyl]tetrasulfide (from Shin-Etsu).

In another embodiment, the poly(isobutylene-co-para-methylstyrene)polymer is functionalized with sulfur, an activator and a silanecoupling agent.

In another embodiment, the poly(isobutylene-co-para-methylstyrene)polymer is functionalized with sulfur and a vulcanizing accelerator. Ina further embodiment, the vulcanizing accelerator isn-tertiary-butyl-2-benzothiazyl sulfenamide (TBBS).

The inventive compositions may include thepoly(isobutylene-co-para-methylstyrene) polymer in an amount of from 5phr to 30 phr, or from 5 phr to 25 phr, or from 10 phr to 20 phr.

Poly(Isobutylene-Co-Para-Methylstyrene-Co-Isoprene) Terpolymer

The term “poly(isobutylene-co-para-methylstyrene-co-isoprene)terpolymer” as used in the specification means a terpolymer comprisingisobutylene, para-methylstyrene and isoprene polymers.

The term “poly(isobutylene-co-para-methylstyrene-co-isoprene)terpolymer” also encompasses functionalizedpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer compoundsdescribed herein.

In one embodiment, thepoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer containsfrom 4-8 mol% p-methylstyrene, 0.2-2 mol% isoprene and 90-95 mol%isobutylene based on the terpolymer.

In one embodiment, thepoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur.

In another embodiment, thepoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and an activator. In a further embodiment,the activator is zinc oxide or stearic acid. In a further embodiment,the activator is a combination of zinc oxide and stearic acid.

In another embodiment, thepoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and a silane coupling agent. In a furtherembodiment, the silane coupling agent isbis(3-triethoxysilylpropyl)tetrasulphide (TESPT) (available as Si69^(Ⓡ)from Evonik Industries) and bis[3-(diethoxyoctyloxysilyl)propyl]tetrasulfide (from Shin-Etsu).

In another embodiment, thepoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur, an activator and a silane coupling agent.

In another embodiment, thepoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and a vulcanizing accelerator. In a furtherembodiment, the vulcanizing accelerator isn-tertiary-butyl-2-benzothiazyl sulfenamide (TBBS).

The inventive compositions may include thepoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer in anamount of from 5 phr to 30 phr, or from 5 phr to 25 phr, or from 10 phrto 20 phr.

Functionalized Polymer

The term “functionalized polymer” as used in the specification means anolefin polymer which has a functional group, such as an epoxy,thioacetate, mercaptothiazole, amine ionomer, phosphine ionomer orcitranellol functional group. Functionalization of a polymer can beimplemented as described herein or as known in the art.

In one embodiment, the functionalized polymer has an epoxy, thioacetate,mercaptobenzothiazole, amine ionomer, phosphine ionomer or citranellolfunctional group.

In a further embodiment, the functionalized polymer has an epoxyfunctional group. Functionalized polymers with an epoxy functional groupcan be prepared by adding 3-chloroperbenzoic acid to a polyolefinpolymer via a reactive mixing process or by the method described herein.In addition to 3-chloroperbenzoic acid, other oxidizing agents may behydrogen peroxide or hypochloride in t-butanol. Preferably, thepolyolefin polymer is a ethylene-propylene-diene terpolymer, butylrubber, poly(isobutylene-co-para-methylstyrene) or apoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer. In afurther embodiment, the epoxy functionalized polymer is epoxidized butylrubber or epoxidized ethylene-propylene-diene terpolymer. In a furtherembodiment, the epoxy functionalized polymer is partially epoxidized.

In a further embodiment, the functionalized polymer has a thioacetatefunctional group. Functionalized polymers with a thioacetate functionalgroup can be prepared by nucleophilic substitution of a polyolefinpolymer with potassium thioacetate by a solution or a reactive mixingprocess. Preferably, the polyolefin polymer is aethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) or apoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer. In afurther embodiment, the thioacetate functionalized polymer isthioacetate functionalized poly(isobutylene-co-para-methylstyrene) orthioacetate functionalized butyl rubber.

In a further embodiment, the functionalized polymer has amercaptobenzothiazole functional group. Functionalized polymers with amercaptobenzothiazole functional group can be prepared by reactingtetrabutyl ammonium bromide (TBAB) and sodium mercaptothiazole with apolyolefin polymer by a reactive mixing process. Preferably, thepolyolefin polymer is a ethylene-propylene-diene terpolymer, butylrubber, poly(isobutylene-co-para-methylstyrene) or apoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer. In afurther embodiment, the mercaptobenzothiazole functionalized polymer ismercaptobenzothiazole functionalizedpoly(isobutylene-co-para-methylstyrene) or mercaptobenzothiazolefunctionalized butyl rubber.

In a further embodiment, the functionalized polymer has an amine ionomerfunctional group. Functionalized polymers with an amine ionomerfunctional group can be prepared by reacting dimethylsoyaalkylamine witha polyolefin polymer by a reactive mixing process or by the methoddescribed herein. Preferably, the polyolefin polymer is aethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) or apoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer. In afurther embodiment, the amine ionomer functionalized polymer ispartially functionalized. In a further embodiment, the amine ionomerfunctionalized polymer is modified BIMSM-amine ionomer or modifiedbutyl-amine ionomer.

In a further embodiment, the functionalized polymer has a phosphineionomer functional group. Functionalized polymers with a phosphineionomer functional group are prepared by reacting diphenyldiphosphinostyrene with a polyolefin polymer by a reactive mixing process.Preferably, the polyolefin polymer is a ethylene-propylene-dieneterpolymer, butyl rubber, poly(isobutylene-co-para-methylstyrene) or apoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer. In afurther embodiment, the phosphine ionomer functionalized polymer ispartially functionalized. In a further embodiment, the phosphine ionomerfunctionalized polymer is modified BIMSM-phosphine ionomer or modifiedbutylphosphine ionomer.

In a further embodiment, the functionalized polymer has a citranellolfunctional group. Functionalized polymers with a citranellol functionalgroup can be prepared by nucleophilic substitution of a polyolefinpolymer with citronellol in a catalyst slurry/sodium alkoxide of sodiumhydride by a solution process. Preferably, the polyolefin polymer is aethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) or apoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer. In afurther embodiment, the citranellol functionalized polymer is a modifiedpoly(isobutylene-co-para-methylstyrene) containing citranellol sidechain substituents.

In a further embodiment, when the polymer is ethylene-propylene-dieneterpolymer or butyl rubber, the functionalized polymer has an epoxy,thioacetate, mercapbenzotothiazole, amine ionomer or phosphine ionomerfunctional group.

In a further embodiment, when the polymer ispoly(isobutylene-co-para-methylstyrene) or apoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer, thefunctionalized polymer has a thioacetate, mercaptobenzothiazole, amineionomer, phosphine ionomer or citranellol functional group.

In a further embodiment, the polymer selected from the group consistingof ethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur.

In another embodiment, the polymer selected from the group consisting ofethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and an activator.

In another embodiment, the polymer selected from the group consisting ofethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and a silane coupling agent.

In another embodiment, the polymer selected from the group consisting ofethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur, an activator and a silane coupling agent.

In another embodiment, the polymer selected from the group consisting ofethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and a vulcanizing accelerator.

Elastomers

The inventive tire tread compositions also comprise an elastomer.Generally the range of the elastomer is from 5 to 75% by weight of thetire tread composition. Suitable elastomers include, for example, dieneelastomers.

“Diene elastomer” is understood to mean, in known manner, an elastomerresulting at least in part (homopolymer or copolymer) from dienemonomers (monomers bearing two double carbon-carbon bonds, whetherconjugated or not).

A diene elastomer can be “highly unsaturated,” resulting from conjugateddiene monomers, which have a greater than 50% molar content of units.

According to one aspect, each diene elastomer having a Tg from -75° C.to 0° C. is selected from the group consisting of natural polyisoprenes,synthetic polyisoprenes having a cis-1,4 linkage content greater than95%, styrene/butadiene/isoprene terpolymers and a mixture of theseelastomers, and each diene elastomer having a Tg from -110° C. to -75°C., preferably from -100° C. to -80° C., is selected from the groupconsisting of polybutadienes having a cis-1,4 linkage content greaterthan 90% and isoprene/butadiene copolymers comprising butadiene units inan amount equal to or greater than 50%.

In one embodiment, the elastomeric composition comprises a dieneelastomer is about 30 to about 70 phr of polybutadiene having a cis-1,4linkage content of at least 95%. In another embodiment, the elastomericcomposition comprises a diene elastomer in about 40 to about 60 phr ofpolybutadiene having a cis-1,4 linkage content of at least 95%.

In another aspect, each diene elastomer having a Tg from -75° C. to 0°C. is selected from the group consisting of natural polyisoprenes andsynthetic polyisoprenes having a cis-1,4 linkage content greater than95%, and each diene elastomer having a Tg from -110° C. to -75° C. is apolybutadiene having a cis-1,4 linkage content greater than 90%, orgreater than 95%.

In one aspect, the composition comprises a blend of at least one of thepolybutadienes having a cis-1,4 linkage content greater than 90% with atleast one of the natural or synthetic polyisoprenes (having a cis-1,4linkage content greater than 95%). An example of a polybutadiene with acis-1,4 linkage content is BUDENEⓇ 1280 available from GoodyearChemical.

These diene elastomers can be classified into two categories:“essentially unsaturated” or “essentially saturated”. The term“essentially unsaturated” is understood to mean generally a dieneelastomer resulting at least in part from conjugated diene monomershaving a level of units of diene origin (conjugated dienes) which isgreater than 15% (mol %); thus it is that diene elastomers such as butylrubbers or copolymers of dienes and of alpha-olefins of EPDM type do notcome within the preceding definition and can in particular be describedas “essentially saturated” diene elastomers (low or very low level ofunits of diene origin, always less than 15%). In the category of“essentially unsaturated” diene elastomers, the term “highlyunsaturated” diene elastomer is understood to mean in particular a dieneelastomer having a level of units of diene origin (conjugated dienes)which is greater than 50%.

Given these definitions, the term diene elastomer capable of being usedherein is understood more particularly to mean: (a) any homopolymerobtained by polymerization of a conjugated diene monomer having from 4to 12 carbon atoms; (b) any copolymer obtained by copolymerization ofone or more conjugated dienes with one another or with one or morevinylaromatic compounds having from 8 to 20 carbon atoms; (c) a ternarycopolymer obtained by copolymerization of ethylene and of analpha-olefin having 3 to 6 carbon atoms with a non-conjugated dienemonomer having from 6 to 12 carbon atoms, such as, for example, theelastomers obtained from ethylene and propylene with a non-conjugateddiene monomer of the abovementioned type, such as, in particular,1,4-hexadiene, ethylidenenorbornene or dicyclopentadiene; (d) acopolymer of isobutene and of isoprene (butyl rubber) and also thehalogenated versions, in particular chlorinated or brominated versions,of this type of copolymer.

The following are suitable in particular as conjugated dienes:1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C₁-C₅alkyl)-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene,2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene or2-methyl-3-isopropyl-1,3-butadiene, an aryl-1,3-butadiene,1,3-pentadiene or 2,4-hexadiene. The following, for example, aresuitable as vinylaromatic compounds: styrene, ortho-, meta- orpara-methylstyrene, the “vinyltoluene” commercial mixture,para-(tert-butyl)styrene, methoxystyrenes, chlorostyrenes,vinylmesitylene, divinylbenzene or vinylnaphthalene.

The copolymers can comprise from 99% to 20% by weight of diene units andfrom 1% to 80% by weight of vinylaromatic units. The elastomers can haveany microstructure which depends on the polymerization conditions used,in particular on the presence or absence of a modifying and/orrandomizing agent and on the amounts of modifying and/or randomizingagent employed. The elastomers can, for example, be block, random,sequential or microsequential elastomers and can be prepared indispersion or in solution; they can be coupled and/or star-branched oralso functionalized with a coupling and/or star-branching orfunctionalization agent. Mention may be made, for coupling to carbonblack, for example, of functional groups comprising a C—Sn bond oraminated functional groups, such as benzophenone, for example; mentionmay be made, for coupling to a reinforcing inorganic filler, such assilica, of, for example, silanol or polysiloxane functional groupshaving a silanol ends, alkoxysilane groups, carboxyl groups, orpolyether groups.

The following are suitable: polybutadienes, in particular those having acontent (molar %) of 1,2-units of from 4% to 80% or those having acontent (molar %) of cis-1,4-units of greater than 80%, polyisoprenes,butadiene/styrene copolymers, a styrene content of from 5% to 60% byweight and more particularly from 20% to 50%, a content (molar %) of1,2-bonds of the butadiene part of from 4% to 75% and a content (molar%) of trans-1,4-bonds of from 10% to 80%, butadiene/isoprene copolymers,in particular those having an isoprene content of from 5% to 90% byweight, or isoprene/styrene copolymers, in particular those having astyrene content of from 5% to 50% by weight. In the case ofbutadiene/styrene/isoprene copolymers, those having a styrene content offrom 5% to 50% by weight and more particularly of from 10% to 40%, anisoprene content of from 15% to 60% by weight and more particularly from20% to 50%, a butadiene content of from 5% to 50% by weight and moreparticularly of from 20% to 40%, a content (molar %) of 1,2-units of thebutadiene part of from 4% to 85%, a content (molar %) of trans-1,4-unitsof the butadiene part of from 6% to 80%, a content (molar %) of 1,2-plus 3,4-units of the isoprene part of from 5% to 70% and a content(molar %) of trans-1,4-units of the isoprene part of from 10% to 50%,and more generally any butadiene/styrene/isoprene copolymer.

The diene elastomer chosen from the group of the highly unsaturateddiene elastomers consisting of polybutadienes (abbreviated to “BR”),synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers,isoprene copolymers and the mixtures of these elastomers.

The term “isoprene elastomer” is understood to mean, in a known way, anisoprene homopolymer or copolymer, in other words a diene elastomerchosen from the group consisting of natural rubber (NR), syntheticpolyisoprenes (IR), the various copolymers of isoprene and the mixturesof these elastomers. Mention will in particular be made, among isoprenecopolymers, of isobutene/isoprene copolymers (butyl rubber IM),isoprene/styrene copolymers (SIR), isoprene/butadiene copolymers (BIR)or isoprene/butadiene/styrene copolymers (SBIR). This isoprene elastomeris preferably natural rubber or a synthetic cis-1,4-polyisoprene; use ispreferably made, among these synthetic polyisoprenes, of thepolyisoprenes having a level (molar %) of cis-1,4-bonds of greater than90%, more preferably still of greater than 98%. One example of a naturalrubber is SVR 3 CV60 available from Standard Vietnamese Rubber CV 60.Another example of a natural rubber is SIR 10 (Standard IndonesianRubber).

The compositions described herein can comprise a single diene elastomeror a mixture of several diene elastomers, it being possible for thediene elastomer or elastomers to be used in combination with any type ofsynthetic elastomer other than a diene elastomer, indeed even withpolymers other than elastomers, for example thermoplastic polymers.

Useful tire tread compositions can comprise, per 100 parts by weight ofrubber (phr), about 30 to about 70 phr of polybutadiene having a cis-1,4linkage content of at least 95%; about 30 to 70 phr of natural rubber orpolyisoprene; about 20 to 50 phr of a processing oil; a curative agent;an antioxidant; about 50 to about 80 phr filler; a silane couplingagent; and about 5 to about 30 phr of a polymer selected from the groupconsisting of ethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer.

Inorganic Fillers

The term “filler” as used herein refers to any material that is used toreinforce or modify physical properties, impart certain processingproperties, or reduce cost of an elastomeric composition.

Examples of preferred filler include, but are not limited to, calciumcarbonate, clay, mica, silica, silicates, talc, titanium dioxide,alumina, zinc oxide, starch, wood flour, carbon black, or mixturesthereof. The fillers may be any size and range, for example in the tireindustry, from 0.0001 µm to 100 µm.

As used herein, the term “silica” is meant to refer to any type orparticle size silica or another silicic acid derivative, or silicicacid, processed by solution, pyrogenic, or the like methods, includinguntreated, precipitated silica, crystalline silica, colloidal silica,aluminum or calcium silicates, fumed silica, and the like. Precipitatedsilica can be conventional silica, semi-highly dispersible silica, orhighly dispersible silica. A preferred filler is commercially availableby Rhodia Company under the trade name ZEOSIL™Z1165.

In one embodiment, the elastomeric composition comprises, per 100 partsby weight of rubber (phr), about 50 to 80 phr filler. In anotherembodiment, the elastomeric composition comprises, per 100 parts byweight of rubber (phr), about 65 to 75 phr filler.

In another embodiment, the elastomeric composition comprises, per 100parts by weight of rubber (phr), about 65 to 70 phr silica.

Use may be made of any type of reinforcing filler known for itscapabilities of reinforcing a rubber composition which can be used forthe manufacture of tires, for example an organic filler, such as carbonblack, a reinforcing inorganic filler, such as silica, or a blend ofthese two types of filler, in particular a blend of carbon black andsilica.

All carbon blacks, in particular blacks of the HAF, ISAF or SAF type,conventionally used in tires (“tire-grade” blacks) are suitable ascarbon blacks. Mention will more particularly be made, among the latter,of the reinforcing carbon blacks of the 100, 200 or 300 series (ASTMgrades), such as, for example, the N115, N134, N234, N326, N330, N339,N347 or N375 blacks, or also, depending on the applications targeted,the blacks of higher series (for example, N660, N683 or N772). Thecarbon blacks might, for example, be already incorporated in theisoprene elastomer in the form of a masterbatch (see, for example,International Applications WO 97/36724 or WO 99/16600). Preferably thecarbon black is VulcanⓇ3 N330 from Cabot Corp.

The term “reinforcing inorganic filler” should be understood, in thepresent patent application, by definition, as meaning any inorganic ormineral filler, whatever its color and its origin (natural orsynthetic), also known as “white filler”, “clear filler” or even“non-black filler”, in contrast to carbon black, capable of reinforcingby itself alone, without means other than an intermediate couplingagent, a rubber composition intended for the manufacture of tires, inother words capable of replacing, in its reinforcing role, aconventional tire-grade carbon black; such a filler is generallycharacterized, in a known way, by the presence of hydroxyl (--OH) groupsat its surface.

The physical state under which the reinforcing inorganic filler isprovided is not important, whether it is in the form of a powder, ofmicrobeads, of granules, of beads or any other appropriate densifiedform. Of course, the term reinforcing inorganic filler is alsounderstood to mean mixtures of different reinforcing inorganic fillers,in particular of highly dispersible siliceous and/or aluminous fillersas described below.

Mineral fillers of the siliceous type, in particular silica (SiO₂), orof the aluminous type, in particular alumina (Al₂O₃), are suitable inparticular as reinforcing inorganic fillers. The silica used can be anyreinforcing silica known to a person skilled in the art, in particularany precipitated or pyrogenic silica exhibiting a BET surface and a CTABspecific surface both of less than 450 m²/g, preferably from 30 to 400m²/g. Mention will be made, as highly dispersible (“HDS”) precipitatedsilicas, for example, of the ULTRASIL™ 7000 and ULTRASIL™ 7005 silicasfrom Degussa, the ZEOSIL™ 1165 MP, C5 MP and 1115 MP silicas fromRhodia, the HI-SIL™ EZ150G silica from PPG, the Zeopol 8715, 8745 and8755 silicas from Huber or silicas with a high specific surface.

In one embodiment, the silica is alone or a combination of silicacompounds. In another embodiment, the silica is not a combination ofsilica compounds. In another embodiment, when the silica is acombination of silica compounds, one of the silica compounds has a BETsurface of from 110 to 175 m²/g.

Mention may also be made, as other examples of inorganic filler beingcapable of being used, of reinforcing aluminum (oxide), hydroxides,titanium oxides or silicon carbides (see, for example, InternationalApplication No. WO 02/053634 or U.S. Publication No. 2004/0030017).

In one embodiment, the inorganic filler is not magnesium sulphate.

When the compositions of the invention are intended for tire treads witha low rolling resistance, the reinforcing inorganic filler is silica,preferably with a BET surface of from 45 to 400 m²/g, more preferably offrom 60 to 300 m²/g. In one embodiment, the silica has a BET surface offrom 110 to 175 m²/g.

Coupling Agent

As used herein, the term “coupling agent” is meant to refer to any agentcapable of facilitating stable chemical and/or physical interactionbetween two otherwise non-interacting species, e.g., between a fillerand a diene elastomer. Coupling agents cause silica to have areinforcing effect on the rubber. Such coupling agents may be pre-mixed,or pre-reacted, with the silica particles or added to the rubber mixduring the rubber/silica processing, or mixing, stage. If the couplingagent and silica are added separately to the rubber mix during therubber/silica mixing, or processing stage, it is considered that thecoupling agent then combines in situ with the silica.

The coupling agent may be a sulfur-based coupling agent, an organicperoxide-based coupling agent, an inorganic coupling agent, a polyaminecoupling agent, a resin coupling agent, a sulfur compound-based couplingagent, oxime-nitrosamine-based coupling agent, and sulfur. Among these,preferred for a rubber composition for tires is the sulfur-basedcoupling agent.

In an embodiment, the coupling agent is at least bifunctional.Non-limiting examples of bifunctional coupling agents includeorganosilanes or polyorganosiloxanes. Other examples of suitablecoupling agents include silane polysulfides, referred to as“symmetrical” or “unsymmetrical” depending on their specific structure.Silane polysulphides can be described by the formula (V):

in which x is an integer from 2 to 8 (preferably from 2 to 5); the Asymbols, which are identical or different, represent a divalenthydrocarbon radical (preferably a C₁-C₁₈ alkylene group or a C₆-C₁₂arylene group, more particularly a C₁-C₁₀, in particular C₁-C₄,alkylene, especially propylene); the Z symbols, which are identical ordifferent, correspond to one of the three formulae (VI):

in which the R¹ radicals, which are substituted or unsubstituted andidentical to or different from one another, represent a C₁-C₁₈ alkyl,C₅-C₁₈ cycloalkyl or C₆-C₁₈ aryl group (preferably C₁-C₆ alkyl,cyclohexyl or phenyl groups, in particular C₁-C₄ alkyl groups, moreparticularly methyl and/or ethyl); the R² radicals, which aresubstituted or unsubstituted and identical to or different from oneanother, represent a C₁-C₁₈ alkoxyl or C₅-C₁₈ cycloalkoxyl group(preferably a group selected from C₁-C₈ alkoxyls and C₅-C₈cycloalkoxyls, more preferably still a group selected from C₁-C₄alkoxyls, in particular methoxyl and ethoxyl).

Non-limiting examples of silane polysulphides includebis((C₁-C₄)alkoxy(C₁-C₄)alkylsilyl(C₁-C₄)alkyl)polysulphides (inparticular disulphides, trisulphides or tetrasulphides), such as, forexample, bis(3-trimethoxysilylpropyl) orbis(3-triethoxysilylpropyl)polysulphides. Further examples includebis(3-triethoxysilylpropyl)tetrasulphide (TESPT) of formula[(C₂H₅O)₃Si(CH₂)₃S₂]₂, or bis(triethoxysilylpropyl)disulphide (TESPD) offormula [(C₂H₅O)₃Si(CH₂)₃S]₂. Other examples include bis(mono(C₁-C₄)alkoxyldi(C₁-C₄)alkylsilylpropyl)polysulphides (inparticular disulphides, trisulphides or tetrasulphides), moreparticularly bis(monoethoxydimethylsilylpropyl)tetrasulphide. Examplesof silane coupling agents are TESPT (Si69Ⓡ from Evonik Industries) andbis[3-(diethoxy octyloxysilyl)propyl]tetrasulfide (an experimentalproduct from Shin-Etsu).

The coupling agent can also be bifunctional POSs (polyorganosiloxanes),or hydroxysilane polysulphides, or silanes or POSs bearing azodicarbonylfunctional groups. The coupling agent can also include other silanesulphides, for example, silanes having at least one thiol (—SH)functional group (referred to as mercaptosilanes) and/or at least onemasked thiol functional group.

The coupling agent can also include combinations of one or more couplingagents such as those described herein, or otherwise known in the art. Apreferred coupling agent comprises alkoxysilane or polysulphurizedalkoxysilane. A particularly preferred polysulphurized alkoxysilane isbis(triethoxysilylpropyl) tetrasulphide, which is commercially availableby Degussa under the trade name X50S™.

In one embodiment, the elastomeric composition of the present invention,the polymer selected from the group consisting ofethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and a silane coupling agent. In a furtherembodiment, the silane coupling agent is selected from the groupconsisting of triethoxysilylpropyl)tetrasulphide, bis[3-(diethoxyoctyloxysilyl)propyl]tetrasulfide and bis(triethoxysilylpropyl)tetrasulphide.

Plasticizer and Resin

As used herein, the term “plasticizer” (also referred to as a processingoil), refers to a petroleum derived processing oil and syntheticplasticizer. Such oils are primarily used to improve the processabilityof the composition. Suitable plasticizers include, but are not limitedto, aliphatic acid esters or hydrocarbon plasticizer oils such asparaffinic oils, aromatic oils, naphthenic petroleum oils, andpolybutene oils. A particularly preferred plasticizer is naphthenic oil,which is commercially available from Nynas under the trade name NYTEX™4700.

MES and TDAE oils are well known to a person skilled in the art; forexample, reference is made to publication KGK (Kautschuk GummiKunstoffe), 52nd year, No. 12/99, pp. 799-805, entitled “Safe ProcessOils for Tires with Low Environmental Impact”.

Mention may be made, as examples of MES oils (whether they are of the“extracted” or “hydrotreated” type) or of TDAE oils, for example, of theproducts sold under the names FLEXON™ 683 by ExxonMobil, VIVATEC™ 200 orVIVATEC™ 500 by H&R European, PLAXOLENE™ MS by Total, or CATENEX™ SNR byShell.

The resins (it should be remembered that the term “resin” is reserved bydefinition for a solid compound) formed of C₅ fraction/vinylaromaticcopolymer, in particular of C₅ fraction/styrene or C₅ fraction/C₉fraction copolymer, are well known; they have been essentially used todate for application as tackifying agents for adhesives and paints butalso as processing aids in tire rubber compositions. An example of ahydrocarbon resin is Oppera™ PR373 from ExxonMobil Chemical Co. Anotherexample of a hydrocarbon resin is Escorez™ E5320 from ExxonMobilChemical Co.

In one embodiment, the elastomeric composition of the present inventioncomprises about 1 to 25 phr hydrocarbon resin. In another embodiment,the elastomeric composition of the present invention comprises about 5to 20 phr hydrocarbon resin.

Other suitable plasticizers for use in the present invention include“triesters” or “fatty acids.” Triester and fatty acid generally refer toa mixture of triesters or a mixture of fatty acids, respectively. Thefatty acid preferably consists of more than 50%, more preferably to morethan 80% by weight of an unsaturated C18 fatty acid, that is to say oneselected from among the group consisting of oleic acid, linoleic acid,linolenic acid and mixtures thereof. More preferably, be it synthetic ornatural in origin, the fatty acid used is constituted to more than 50%by weight, more preferably still to more than 80% by weight, of oleicacid.

In other words, very particularly a glycerol trioleate, derived fromoleic acid and glycerol, is used. Among the preferred glyceroltrioleates, mention will be made in particular, as examples of naturalcompounds, of the vegetable oils sunflower oil or rapeseed oil having ahigh content of oleic acid (more than 50%, more preferably more than 80%by weight).

The glycerol triester is used in a preferred amount of between 5 and 80phr, more preferably of between 10 and 50 phr, in particular within arange from 15 to 30 phr, in particular when the tread of the inventionis intended for a passenger-type vehicle. In the light of the presentdescription, the person skilled in the art will be able to adjust thisamount of ester as a function of the specific conditions of embodimentof the invention, in particular the amount of inorganic filler used.

Antidegradants

Antidegradants encompass antioxidants, antiozonants and waxes.Antiozonanats are used to protect rubber products from ozone. Waxes arealso used to provide rubber ozone protection. An example of an antiozonewax is AKROWAX™ 5084 from AkroChem.

As used herein, the term “antioxidant” refers to a chemical that combatsoxidative degradation. Suitable antioxidants includediphenyl-p-phenylenediamine and those disclosed in The Vanderbilt RubberHandbook (1978), Pages 344 to 346. A particularly preferred antioxidantis para-phenylenediamines, which is commercially available by Eastmanunder the trade name SANTOFLEX™ 6PPD(N-(1,3-Dimethylbutyl)-N′-phenyl-1,4-phenylenediamine). Anotherpreferred antioxidant is a high-molecular-weight, hindered amine lightstabilizer, which is commercially available as CHIMASSORBⓇ 2020 fromBASF Corp.

Crosslinking Agents, Curatives, Cure Packages, and Curing Processes

The elastomeric compositions and the articles made from thoseelastomeric compositions described herein are generally manufacturedwith the aid of at least one cure package, at least one curative, atleast one vulcanizing or crosslinking agent, and/or undergo a process tocure the elastomeric composition. As used herein, at least one curativepackage refers to any material or method capable of imparting curedproperties to a rubber as is commonly understood in the industry.Preferred crosslinking agents are sulfur, sulfur halides, organicperoxides, quinone dioximes, organic polyvalent amine compounds,methylol group-containing alkylphenol resins and the like are mentioned.A preferred crosslinking agent is sulfur. The amount of sulfur to beblended is preferably from 0.1 to 5 parts by mass and more preferablyfrom 0.5 to 3 parts by mass based on 100 parts by mass of the total ofthe polymer components contained in the polymer composition.

The sulfur may be provided either as free sulfur, through a sulfur donoror combinations thereof. Suitable free sulfur includes, for example,pulverized sulfur, rubber maker’s sulfur, commercial sulfur, andinsoluble sulfur. Examples of sulfur donors are amine disulfides,n-tertiary-butyl-2-benzothiazylsulfenamide (TBBS) (VanaxⓇ NS Rodformfrom Vanderbilt Chemical), tetramethyl thiuram disulfide (AkrochemTMTD), 4,4′-dithiodimorpholine (Akrochem DTDM), dipentamethylene thiuramtetrasulfide (Akrochem DPTT) and thiocarbamyl sulfonamide (AkrochemCure-Rite 18).

In an embodiment, the elastomeric compositions of the present inventioncomprise sulfur fuctionalized polymers, wherein the polymers are furtherfunctionalized with sulfur and a sulfur donor. In a further embodiment,the sulfur donor is selected from the group consisting ofn-tertiary-butyl-2-benzothiazylsulfenamide, tetramethyl thiuramdisulfide, 4,4′-dithiodimorpholine, dipentamethylene thiuramtetrasulfide and thiocarbamyl sulfonamide.

The cure package may also contain various chemicals, additives, and thelike which are commonly used in the rubber industry, as desired.Examples of such chemicals or additives include vulcanizing aids,processing aids, vulcanizing accelerators, process oils, anti-agingagents, anti-scorching agents, zinc oxide, stearic acid, and the like.In one embodiment, zinc oxide is in naphthenic oil such as AKRO-ZINC^(Ⓡ)BAR 85 available from Akrochem Corp.

In another embodiment, the amount of the vulcanizing aid and theprocessing aid to be blended is usually from 0.5 to 5 parts by massbased on 100 parts by mass of the total of the polymer componentscontained in the polymer composition.

Examples of vulcanizing accelerators are sulfenamide-based,guanidine-based, thiuram-based, thiourea-based, benzothiazole-based,dithiocarbamic acid-based, and xanthogenic acid-based compounds, andpreferably include 2-mercaptobenzothiazole, dibenzothiazyl disulfide,N-cyclohexyl-2-benzothiazylsulfenamide,N-t-butyl-2-benzothiazolesulfenamide,N-oxyethylene-2-benzothiazolesulfenamide,N-oxyethylene-2-benzothiazolesulfenamide,N,N′-diisopropyl-2-benzothiazolesulfenamide, diphenylguanidine,diorthotolylguanidine, orthotolylbisguanidine, and the like. Examples ofguanidine-based vulcanizing accelerators are diphenylguanidine (DPG),diorthotolylguanidine (DOTG) and orthotolylbisguanidine.

Examples of dithiocarbamic acid-based vulcanizing accelerators aretetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide(TMTD) and zinc diethylthiocarbamate (ZDEC). Examples ofsulfenamide-based vulcanizing accelerators areN-cyclohexyl-2-benzothiazylsulfenamide (CBS),N-t-butyl-2-benzothiazolesulfenamide (TBBS),N-oxyethylene-2-benzothiazolesulfenamide,N-oxyethylene-2-benzothiazolesulfenamide,N,N′-diisopropyl-2-benzothiazolesulfenamide,2-morpholinothiobenzothiazole (MBS) andN-dicyclohexylbenzothiazole-2-sulfenamide (DCBS). Examples ofbenzothiazole-based vulcanizing accelerators are 2-mercaptobenzothiazole(MBT), dibenzothiazyl disulfide and 2,2′-dithiobisbenzothiazole (MBTS).

Preferably, the vulcanizing accelerator isN-cyclohexyl-2-benzothiazylsulfenamide (CBS) available from KemaiChemical Co. Another preferred vulcanizing accelerator is diphenylguanidine available as Ekaland DPG from MLPC International (Arkema).

The vulcanizing accelerator may be a single vulcanizing accelerator or amixture of accelerators. Preferably, the mixture of accelerators is amixture of different types of accelerators, such as abenzothiazole-based vulcanizing accelerator with a dithiocarbamicacid-based vulcanizing accelerator or a guanidine-based vulcanizingaccelerator.

The amount of the vulcanizing accelerator (or mixture thereof) to beblended is usually from 0.1 to 5 parts by mass and preferably from 0.4to 4 parts by mass based on 100 parts by mass of the total of thepolymer components contained in the polymer composition.

Tire Tread Formulations

In one embodiment, a tire tread composition comprises the elastomericcomposition described herein. In another embodiment, an articlecomprises the tire tread composition described herein. In anotherembodiment, a tread for a winter tire comprises the tire treadcomposition described herein.

The tire tread composition has many desirable properties when thefunctionalized or unfunctionalized polymer selected from the groupconsisting of ethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer ispresent in the elastomeric compositions.

One way of measuring a desirable property of a tread composition is byutilizing the Dynamic Mechanical Thermal Analysis (DMTA) test method.All tire tread compositions were compression molded and cured into pads.Afterward, a rectangular test specimen (12 mm wide & 30 mm long) is diedout of the cured pads and mounted on an ARES G2 (Advanced RheometricExpansion System, TA Instruments) for dynamic mechanical testing intorsion rectangular geometry. Though the thickness of the test specimenis measured manually for each test. A strain sweep at room temperatureup to 5.5% strains and at 10 Hz was conducted first followed by atemperature sweep at 4% strain and 10 Hz from -26° C. to 100° C. at 2°C./min ramp rates. Storage and loss moduli are measured along with theloss tangent values. For better wet traction, it is preferred to havehigher loss tangent values at a temperatures of 0oC. For better rollingresistance, the loss tangent is preferred to be lower at a temperatureof 60° C.

As measured by the DMTA test method, the temperature at which themaximum tan delta occurred is recorded is the glass transitiontemperature, Tg. The maximum Energy Loss (Tangent Delta, wherein theslope is zero) of the immiscible polyolefin domain of the curedcomposition is at a temperature within the range from about -60 to 20°C., preferably at about -60 to -40° C. More preferably, the Tgtemperature is within the range from about -55 to -45° C.

The various descriptive elements and numerical ranges disclosed hereinfor the polymer selected from the group consisting ofethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer, thereactants used to make these polymers, and their use in tire treadcompositions can be combined with other descriptive elements andnumerical ranges to describe the invention(s); further, for a givenelement, any upper numerical limit can be combined with any lowernumerical limit described herein. The features of the invention aredescribed in the following non-limiting examples.

Examples

The features of the invention are described in the followingnon-limiting examples. Preparation of the compounds of Examples 1-11 aredescribed below. However, those skilled in the art will recognize thatother procedures can also be suitable.

Example 1. Preparation of Partially (Ca. 20%) Epoxidized Butyl RubberVia Reactive Mixing Process

All mixing experiments were performed in a Brabender Intelli-torqueinternal mixer using roller type 6 blades. The mixer temperature was setto 70° C. 60 g of Butyl 365 (ExxonMobil Chemical) was fluxed for 30seconds at 25 rpms, 1.3 g of 3-chloroperbenzoic acid (Aldrich, <77%purity) was added slowly to the mixer. Once addition is complete, thecompound was mixed for 10-12 minutes at 60 rpms. The epoxidized Butylproduct was removed from the mixer and cooled to room temperature bypressing between two Teflon sheets in a Carver press.

The partially (ca. 20%) epoxidized Butyl product was characterized usingproton NMR spectroscopy showing the oxirane proton at 2.7 ppm, and theremaining isoprene olefinic protons at 4.97 and 5.05 ppm.

The ¹H-NMR spectra of the partially epoxidized butyl rubber obtained viareactive mixing (Example 1) is disclosed at FIG. 1 .

General ¹H-NMR Test Method for the Examples on This Invention

In a glass vial, add 50 mg of sample and ~1 mL of 99.8% CDCl₃ with 0.03%(v/v) TMS. Place on wrist action shaker until completely dissolved ~2hours. Transfer the solution to a new NMR tube (using DeuterotubesBORO400-5-7) ensuring that all sample is dissolved and there are nosolids remaining. Run the PROTON experiment on the Bruker 500 MHz NMRlocked onto CDCl₃ as the solvent and using the standard parametersbelow:

-   NUC: 1H-   DS: 2-   NS:16-   TD0: 1-   AQ: 3.27 seconds-   SW: 19.99 ppm or 10,000 Hz-   Zg30 is a 30° pulse; 5 mm probe, 16 scans, 1s delay, 500 MHz.

Analyze the spectra using MestReNova software. Perform a manual phasecorrection and baseline correction before integration.

Example 2. Preparation of Partially (Ca. 20%) EpoxidizedEthylene-Propylene-Diene Terpolymer Via Reactive Mixing Process

All mixing experiments were performed in a Brabender Intelli-torqueinternal mixer using roller type 6 blades. The mixer temperature was setto 70° C. 60 g of ethylene-propylene-diene terpolymer (90.6 wt% C3, 6.9wt% C2, 2.5 wt% ENB) was fluxed for 30 seconds at 25 rpms, 0.56 g of3-chloroperbenzoic acid (Aldrich, <77% purity) was added slowly to themixer. Once addition is complete, the compound was mixed for 10-12minutes at 60 rpms. The epoxidized ethylene-propylene-diene terpolymerproduct was removed from the mixer and cooled to room temperature bypressing between two Teflon sheets in a Carver press.

The partially epoxidized (ca. 20%) ethylene-propylene-diene terpolymerproduct was characterized using proton NMR spectroscopy showing theoxirane proton at 3.09 ppm, and the ENB olefinic protons at 5.21 and5.01 ppm.

The ¹H-NMR spectra of partially epoxidized ethylene-propylene-dieneterpolymer obtained by a reactive mixing process (Example 2) isdisclosed at FIG. 2 .

Example 3: Preparation of Thioacetate FunctionalizedPoly(Isobutylene-Co-Para-Methylstyrene) by Solution Process

Nucleophilic substitution reaction of potassium thioacetate with Exxpro™(NPX 1602) was conducted in a 50 L glass reactor equipped with a stirrerand chiller. Dry Tetrahydrofuran (THF) (water ppm ≤ 10 ppm) was preparedby passing 99 % THF (Sigma Aldrich) through 3A molecular sieve. 4000 gof Exxpro™ (Mn = 221000 g/mole; 5002 g/mole Br; 0.799 mole) was added tothe 50 L reactor under nitrogen blanket. The polymer was dissolved inthe already prepared dry THF (38 L) at constant stirring at 25° C. for12 hours or until the polymer is dissolved. A slurry of 2.96 mole (260g) of potassium thioacetate, was prepare with 1 L of dry THF. The slurrywas added to the polymer solution slowly, with constant stirring. Thereaction mixture was held at 25° C. for 24 h. At the end of thestipulated time, the reaction mixture is introduced into the quench potcontaining 100 L of isopropanol, to precipitate the functionalizedpolymer. The ppt. polymer was re-dissolved in a reactor containing 20 Lof isohexane and 2 wt% of Butylated hydroxytoluene (BHT; Sigma Aldrich).The re-dissolved polymer was introduced into the 50 L steam strippingpot, connected with a condenser and a chiller. The steam stripping isdone using 20 Kg/h of steam under nitrogen blanket. The steam strippedfunctionalized polymer was finally dried using heated roll mill toobtain 4200 g of functionalized Exxpro™.

The dried polymer was characterized using proton NMR spectroscopy &FTIR. Complete conversion was achieved in 24 h.

The thioacetate functionalized poly(isobutylene-co-para-methylstyrene)product was characterized using proton NMR spectroscopy showing completedisappearance of methylene proton (— CH₂Br), with new resonanceappearing at 4.09 ppm for ~ CH₂S—COCH₃

The ¹H-NMR spectra of the thioacetate functionalizedpoly(isobutylene-co-para-methylstyrene) obtained by a solution process(Example 3) is disclosed at FIG. 3 .

Example 4: Preparation of Thioacetate Functionalized Butyl Rubber by aReactive Mixing Process

All reactive mixing experiments were performed in a BrabenderIntelli-torque internal mixer using roller type 6 blades. The mixertemperature was set to between 120-150° C. 60 g of Bromobutyl 2222(ExxonMobil Chemical) was added to mixer and allowed to flux for 30seconds at 25 rpm, ca. 1 g of tetrabutyl ammonium bromide (TBAB) and ca.1.69 -1.78 g (1.20 - 1.26 mol. equiv. to allylic-Br) of potassiumthioacetate. The mixing speed was set to 60 rpm and the reactive mixingwas also done sequentially by adding TBAB first and allowed to mix for10-15 minutes, then potassium thioacetate was added and allowed to mixfurther for 10-15 minutes. The final mix was removed from the mixer andcooled to room temperature by pressing between two Teflon sheets in aCarver press. The final products was obtained in quantitative yield withca. >80% conversion by ¹H-NMR analysis.

The ¹H-NMR spectra of the thioacetate functionalized butyl rubberobtained by a reactive mixing process (Example 4) is disclosed at FIG. 4.

Example 5: Preparation of Mercaptobenzothiazole FunctionalizedPoly(Isobutylene-Co-Para-Methylstyrene) by a Reactive Mixing Process

All reactive mixing experiments were performed in a BrabenderIntelli-torque internal mixer using roller type 6 blades. The mixertemperature was set to between 70-120° C. 60 g of BIMSM (Exxpro™ NPX1602 from ExxonMobil Chemical) was added to mixer and allowed to fluxfor 30 seconds at 25 rpm, 0.45 g (0.11 mol. equiv. to PMS-Br) oftetrabutyl ammonium bromide (TBAB) and 3.09 g (1.25 mol. equiv. toPMS-Br) of sodium mercaptothiazole. The mixing speed was set to 60 rpmand allowed to mix for 15 minutes. The final mix was removed from themixer and cooled to room temperature by pressing between two Teflonsheets in a Carver press. The final product was obtained in quantitativeyield with >92% conversion by ¹H-NMR analysis.

The ¹H-NMR spectrum of the mercaptobenzothiazole functionalizedpoly(isobutylene-co-para-methylstyrene) (Example 5) obtained by areactive mixing process is disclosed at FIG. 5 .

Example 6: Preparation of Mercaptobenzothiazole Functionalized ButylRubber by a Reactive Mixing Process

All reactive mixing experiments were performed in a BrabenderIntelli-torque internal mixer using roller type 6 blades. The mixertemperature was set to between 70-120° C. 60 g of Bromobutyl 2222(ExxonMobil Chemical) was added to mixer and allowed to flux for 30seconds at 25 rpm, 0.45 g of tetrabutyl ammonium bromide (TBAB) and 2.94g (ca. 1.20 mol. equiv. to allylic-Br) of sodium mercaptothiazole. Themixing speed was set to 60 rpm and allowed to mix for 15-30 minutes. Thefinal mix was removed from the mixer and cooled to room temperature bypressing between two Teflon sheets in a Carver press. The final productwas obtained in quantitative yield with >94% conversion by ¹H-NMRanalysis.

The ¹H-NMR spectra of the mercaptobenzothiazole functionalized butylrubber obtained by a reactive mixing process (Example 6) is disclosed atFIG. 6 .

Example 7: Preparation of Modified BIMSM-Amine Ionomer Via ReactiveMixing Process

All mixing experiments were performed in a Brabender Intelli-torqueinternal mixer using roller type 6 blades. The mixer temperature was setto 120° C. 60 g of BIMSM (Exxpro™ NPX 1602 from ExxonMobil Chemical)elastomer

was fluxed for 30 seconds at 60 rpms, 0.5 g (0.13 mol equiv.) of ArmeenDMSVD from AkzoNobel was added slowly to the mixer. Once addition iscomplete, the compound was mixed for 10-12 minutes at 60 rpms. Themodified Exxpro™ product mixture was removed from the mixer and cooledto room temperature by pressing between two Teflon sheets in a Carverpress.

The resulting BIMSM-amine ionomer product derived from a dimethylsoyaalkylamine (Armeen DMSVD from AkzoNobel) was characterized usingproton NMR spectroscopy showing both the methylene proton (~ CH₂Br),along with a new resonance appearing at 5.38 ppm for olefinic signal.

The ¹H-NMR spectra of the BIMSM-amine ionomer obtained by a reactivemixing process (Example 7) is disclosed at FIG. 7 .

Example 8: Preparation of Modified Butyl-Amine Ionomer Via a ReactiveMixing Process

All mixing experiments were performed in a Brabender Intelli-torqueinternal mixer using roller type 6 blades. The mixer temperature was setto 120-150° C. 60 g of Bromobutyl 2222 (ExxonMobil Chemical) was fluxedfor 30 seconds at 60 rpms, 1.41 g (0.54 mol equiv.) of Armeen DMSVD fromAkzoNobel was added slowly to the mixer. Once addition is complete, thecompound was mixed for 10-15 minutes at 60 rpms. The modified butylproduct mixture was removed from the mixer and cooled to roomtemperature by pressing between two Teflon sheets in a Carver press.

The resulting butyl-amine ionomer product was characterized using protonNMR spectroscopy showing both the endo-allylic protons at 4.05, 4.09 ppmalong with a new olefinic peak at 5.38 ppm.

The 1H-NMR spectra of the butyl-amine ionomer obtained by a reactivemixing process (Example 8) is disclosed at FIG. 8 .

Example 9. Preparation of ModifiedPoly(Isobutylene-Co-Para-Methylstyrene) Containing Citranellol SideChain Substituents Via Etherfication Using a Solution Process

Nucleophilic substitution reaction of Citronellol with Exxpro™ NPX 1602(ExxonMobil Chemical) was conducted in a 50 L glass reactor equippedwith a stirrer and chiller. Dry Tetrahydrofuran (THF) (water ppm ≤ 10ppm) was prepared by passing 99% THF (Sigma Aldrich) through 3Amolecular sieve. 4000 g of Exxpro™ (Mn = 221000 g/mole; 5002 g/mole Br;0.799 mole) was added to the 50 L reactor under nitrogen blanket. Thepolymer was dissolved in the already prepared dry THF (38L) at constantstirring at 25° C. for 12 hours or until the polymer is dissolved. Acatalyst slurry/sodium alkoxide of 7.99 mole (320 g) of Sodium Hydride(60% oil), was prepared by adding slowly 1 L of dry THF & 1.45 L (1247g, 8.0 moles) of Citronellol under constant stirring. Once the evolutionof hydrogen gas is complete, the catalyst slurry prepared was addedslowly to the reactor containing dissolved polymer. The reaction mixturewas held at 25° C. for 24 h. At the end of the stipulated time, thereaction mixture is introduced into the quench pot containing 100 L ofisopropanol, to precipitate the functionalized polymer. The ppt. polymerwas re-dissolved in a reactor containing 20 L of isohexane and 2 wt% ofButylated hydroxytoluene (BHT; Sigma Aldrich). The re-dissolved polymerwas introduced into the 50 L steam stripping pot, connected with acondenser and a chiller. The steam stripping is done using 20 Kg/h ofsteam under nitrogen blanket. The steam stripped functionalized polymerwas finally dried using heated roll mill to obtain 4200 g offunctionalized Exxpro™.

The dried polymer was characterized using proton NMR spectroscopy &FTIR. 1H NMR spectroscopy showed complete disappearance of methyleneproton (~ CH2Br), with new resonance appearing at 4.5 ppm for ~ CH2O andolefinic signal at 5.1 ppm suggesting complete conversion at the end of24 h.

The ¹H-NMR spectra of the modifiedpoly(isobutylene-co-para-methylstyrene) containing citranellol obtainedby solution process (Example 9) is disclosed at FIG. 9 . Example 10.Preparation of (isobutylene-co-isoprene-co-para-methylstyrene)terpolymer.

The IB-IP-PMS terpolymer samples were prepared using standard slurrycationic polymerization technique in a dry box. A premixed para-methylstyrene, isoprene, and isobutylene monomer solution in MeCl was preparedat -95° C. An initiator/co-initiator solution of HCl/EtAlCl₂ in MeCl wasalso prepared at -95° C.

The initiator/co-initiator solution was added slowly into mixed monomersolution with stirring.

After approximately 5-10 minutes, the reaction was quenched with a smallaliquot of isopropyl alcohol. The resulting polymer was obtained bycoagulation with isopropyl alcohol and further dried in a vacuum oven at50° C. overnight. The overall monomer conversion was approximately about62 to 82%.

Composition (mol%) Terpolymer 1 p-methylstyrene 6.57 isoprene 0.45isobutylene 92.97

Isobutylene-co-isoprene-co-para-methylstyrene terpolymer 1 contained6.57 mol% p-methylstyrene, 0.45% mol% isoprene and 92.97 mol%isobutylene. The ¹H-NMR spectra ofpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer 1 isdisclosed at FIG. 10 .

¹H-NMR Τest Μethod for Isobutylene-Isoprene-p-methylstyrene Τerpolymer

¹H NMR samples were prepped at room temperature in CDCl₃ (deuteratedchloroform) with a concentration of 20 mg/ml.

Samples were run under the following conditions, magnetic field of atleast 500 MHz, 5 mm probe, 25° C., 30° tip angle, 800 transients, and a5 second delay. Reference to isobutylene CH₃ peak at 1.12 ppm.

Proton NMR peak assignment for Isobutylene-Isoprene-p-methylstyreneterpolymer Name Shift # Protons I_(PIB) 0.5-1.17 ppm 6 I_(1,4) Isoprene5.02-5.16 ppm 1 I_(Minor) _(isoprene) 4.92-4.97 ppm 1 I_(PMS) 6.2-7.2ppm 4 I=intensity/ area PIB=IPIB/6 1,4= I1,4 isoprene Minor= Iminorisoprene PMS=IPMS/4 Total=PIB+1,4+minor+PMS Mole % PIB =PIB/total^(∗)100Mole % 1,4=1,4/total*100 Mole % PMS=PMS/total^(∗)100

Example 11. Preparation of Amorphous Propylene-Based Copolymers

Catalyst system: Catalyst precursor wasbis((4-triethylsilyl)phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium dimethyl. However, other metallocene precursors with good dieneincorporation and MW capabilities could also be used.

The activator was dimethylanilinium tetrakis(pentafluorophenyl)borate,but dimethylanilinium-tetrakis(heptafluoronaphthyl)borate and othernon-coordinating anion type activators or MAO could also be used.

The copolymer compositions were synthesized in a single continuousstirred tank reactor. A mixture containing unreacted monomers andsolvent was fed to the reactor as fuel for a polymerization reaction.The polymerization was performed in solution using isohexane as solvent.During the polymerization process, hydrogen addition and temperaturecontrol were used to achieve the desired melt flow rate. The catalyst,activated externally to the reactor, was added as needed in amountseffective to maintain the target polymerization temperature.

In the reactor, the copolymer material was produced in the presence ofethylene, propylene, ethylidene norbornene, and a catalyst comprisingthe reaction product of N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate and[cyclopentadienyl(2,7-di-t-butylfluorenyl)di-p-triethylsilanephenylmethane]hafnium dimethyl.

The copolymer solution emerging from the reactor was quenched and thendevolatilized using conventionally known devolatilization methods, suchas flashing or liquid phase separation, first by removing the bulk ofthe isohexane to provide a concentrated solution, and then by strippingthe remainder of the solvent in anhydrous conditions using adevolatilizer so as to end up with a molten polymer compositioncontaining less than 0.5 wt% of solvent and other volatiles. The moltenpolymer composition was advanced by a screw to a pelletizer from whichthe polymer composition pellets are submerged in water and cooled untilsolid.

The ethylene-propylene-diene terpolymer (EPDM) was characterized usingproton and carbon NMR spectroscopy.

Composition (wt%) EPDM 1 EPDM 2 C3 (propylene) 81.9 90.6 C2 (ethylene)15.3 6.9 ENB 2.8 2.5

Ethylene-propylene-diene terpolymer, EPDM 1, contained 81.9 wt%propylene, 15.3 wt% ethylene and 2.8 wt% 5-ethylidene-2-norbornene(ENB). EPDM 2 contained 90.6 wt% propylene, 6.9 wt% ethylene and 2.5 wt%ENB. The two ethylene-propylene-diene terpolymers differed in theirratio of propylene to ethylene. EPDM 1 contained more ethylene whileEPDM 2 contained more propylene. The ¹H-NMR spectra of EPDM 1 isdisclosed at FIG. 11 .

¹H-NMR Test Method for EthylenePropylene-Diene Polymer (EPDM)

For ¹H NMR, sample preparation (polymer dissolution) was performed at140° C. where 20 miligrams of polymer was dissolved in an appropriateamount of solvent to give a final polymer solution volume of 1 ml.

The ¹H solution NMR was performed on a 5 mm probe at a field of at least500 MHz in an ODCB (ortho-dichlorobenzene) and benzene-d6 (C₆D₆) mixture(9:1) at 120° C. with a flip angle of 30°, 15s delay, and 512transients. Chemical shifts were referenced to the ODCB peak at 7.22ppm. Signals were integrated and the 2-ethylidene-5-norbornene (ENB)weight percent was reported.

Calculation of ENB and double bonds was performed as shown below:

-   Imajor= Integral of major ENB species from 5.2-5.4 ppm-   Iminor= Integral of minor ENB species from 4.6-5.12 ppm-   Ialiph= (Integral of —CH₂— from 0-3 ppm)-   total= (ENB+EP)-   total wt = (ENB^(∗)120+EP^(∗)14)

Proton NMR peak assignment for EPDM Peak Assignments Intensity ofspecies MOLE % WEIGHT % Olef: 5.3 and 5.1 ppm ENB ENB= I_(major) +I_(minor) ENB*100/total ENB*120*100/total wt Aliphatic: 3 - 0 ppm EP=(I_(aliph)-11^(∗)ENB)/2 EP*100/total EP*14*100 /total wt

The ¹³C solution NMR was performed on a 10 mm cryopprobe of at least 600MHz in an ODCB (ortho-dichlorobenzene) and benzene-d6 (C₆D₆) mixture(9:1) at 120° C. with a flip angle of 90° and inverse gated decoupling.Sample preparation (polymer dissolution) was performed at 140° C. where0.20 grams of polymer was dissolved in an appropriate amount of solventto give a final polymer solution volume of 3 ml. Chemical shifts werereferenced to the ODCB solvent central peak at 130 ppm. ¹³C NMRdetermines the ethylene and propylene composition, not accounting forthe ENB present.

Assignments for ethylene-propylene-diene terpolymers are based on Geertvan der Velden, Macromolecules, 1983, 16, 85-89, and Kolbert et. al.Journal of Applied Polymer Science, 1999, 71, 523-530.

Examples 12 to 32 Additive Formulations

TABLE 1 lists the functionalized polymers and their respective additiveformulation Polymer Base Compound ID Example Polymer Example DescriptionAdditive Formulation Poly(isobutylene-co-para-methylstyrene) (Exxpro) 125 Exxpro-mercaptothiazole 1 13 7 Exxpro-amine ionomer 1 14 3Exxpro-thioacetate 2 15 9 Exxpro-citronellol 2 16 Experimental product(1.3 mol% halogen, 9.5 wt% para-methylstyrene) Exxon Exxpro NPX 1602 1Butyl 17 6 Bromobutyl-Mercaptothiazole 1 18 8 Bromobutyl-amine ionomer 119 4 Bromobutyl thioacetate 2 20 Commercial product Exxon Bromobutyl2222 1 21 Commercial product Exxon SBB 6222 1 22 Commercial productExxon Chlorobutyl 1066 1 23 Commercial product Exxon Butyl 365 3 24Commercial product Exxon Butyl 065 2 25 Commercial product Exxon Butyl065 5 26 1 Epoxidized Butyl 2 EPDM 27 2 Epoxidized EPDM 2 28 11 EPDM 1 229 11 EPDM 1 4 30 11 EPDM 2 5 31 11 EPDM 1 3 IB-IP-PMS Terpolymer 32 10Terpolymer 1 2

The following additive formulations were used for Examples 12-32. Allcomponents are listed in phr, or part per hundred, of polymer unit.These compounds were mixed in suitable mixers, using one pass ormultiple successive passes well known to the person skilled in the art.The mixing temperatures range between 110° C. and 210° C. The durationof the mixing for each of the individual mixing steps is between 1 and30 minutes depending on desired property. The amounts of components inthe Additive Formulations are listed in the table below.

Ingredient Additive Formulation 1 (phr) Additive Formulation 2 (phr)Additive Formulation 3 (phr) Additive Formulation 4 (phr) AdditiveFormulation 5 (phr) Polymer Listed in Table 1 100 100 100 100 100 N330carbon black (VulcanⓇ 3 from Cabot 8 8 2.5 8 8 Corp.)High-molecular-weight, hindered amine light stabilizer (CHIMASSORBⓇ 2020from BASF Corp.) 0.8 0.8 0.8 0.8 0.8 Super fine sulfur (Rubbermakersfrom Harwick Standard Distribution Corp.) 2.5 2.5 2.5 2.5 2.5 Zinc oxidein naphthenic oil (AKRO-ZINC® BAR 85 from Akrochem Corp.) 1 1 Stearicacid (97% stearic acid from Acros Organics) 1 1 50:50 blend of Si69Ⓡ andN330 carbon black (X50-SⓇ from Evonik Industries) 10.5 Bis[3-(diethoxyoctyloxysilyl) propyl] tetrasulfide (Experimental product fromShin-Etsu) 3.2 N-tertiary-butyl-2-benzothiazyl sulfenamide (TBBS)(Vanax® NS Rodform from Vanderbilt Chemical) 0.75 1.5 Total PHR 111.3113.3 118.3 115.25 112.8

Tread Formulations

Tire tread compound formulations are listed in the tables below. Allcomponents are listed in phr, or part per hundred, of polymer unit.These compounds were mixed in suitable mixers, using at least twosuccessive passes well known to the person skilled in the art. Thenon-productive passes (mixing without crosslinking system) which havemixing at high temperatures between 110° C. and 190° C. Thenon-productive passes are followed by a productive pass where thecrosslinking system is added. The temperature for this mixing istypically below 110° C. The duration of the mixing for each of theindividual mixing steps is between 1 and 20 minutes.

Examples of tire tread low filler formulations are listed in the tablebelow as tread formulations TT1 to TT9. Tread compound controls with noTable 1 polymer additive are tread formulations TT1 and TT9.

Tire Tread Formulations (TT1-TT9) Ingredient TT1 TT2 TT3 TT4 TT5 TT6 TT7TT8 TT9 NR (1) 50 50 50 50 50 50 50 50 50 Silica (2) 65 65 65 65 65 6565 65 65 BR (3) 50 50 50 50 50 50 50 50 50 Coupling agent (4) 5.2 5.25.2 5.2 5.2 5.2 5.2 5.2 5.2 Plasticizing agent (5) 35 35 35 35 35 35 3535 35 Antioxidant (6) 2 2 2 2 2 2 2 2 2 Carbon black (7) 5 5 5 5 5 5 5 55 Stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Ex. 12 20 Ex. 13 20Ex. 14 20 Ex. 15 20 Ex. 16 20 Ex. 32 20 Ex. 27 20 ZnO (8) 2 2 2 2 2 2 22 2 Accelerator 1 (9) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Sulfur 1.2 1.21.2 1.2 1.2 1.2 1.2 1.2 1.2 Accelerator 2 (10) 1.8 1.8 1.8 1.8 1.8 1.81.8 1.8 1.8 Total PHR 221.5 241.5 241.5 241.5 241.5 241.5 241.5 241.5221.5 (1) Natural rubber SIR 10 (Standard Indonesian Rubber) (2)Amorphous Silica (ZEOSILⓇ 1165MP from Rhodia) (3) High-cis BR (BUDENEⓇ1280 from Goodyear Chemical) (4) Silane coupling agent TESPT (Si69Ⓡ fromEvonik Industries) (5) High viscosity naphthenic black oil (NYTEXⓇ 4700from Nynas AB) (6) N-(1,3-Dimethylbutyl)-N′-phenyl-p-phenylenediamine(Santoflex^(Ⓡ) 6-PPD from Flexsys) (7) Carbon black (VulcanⓇ3 N330 fromCabot Corp.) (8) Zinc oxide in naphthenic oil (AKRO-ZINCⓇ BAR 85 fromAkrochem Corp.) (9) N-cyclohexyl-2-benzothiazylsulfenamide (CBS fromKemai Chemical Co.) (10) Diphenyl guanidine (Ekaland DPG from MLPCInternational (Arkema)

A second set of low filler tread compound formulations are listed belowas tire tread formulations TT10 to TT19. Tread compound controls with noTable 1 polymer additive are tread formulations TT10 and TT19.

Tire Tread Formulations (TT10 to TT19) Ingredient TT10 TT11 TT12 TT13TT14 TT15 TT16 TT17 TT18 TT19 NR (1) 50 50 50 50 50 50 50 50 50 50Silica (2) 65 65 65 65 65 65 65 65 65 65 BR (3) 50 50 50 50 50 50 50 5050 50 Coupling agent (4) 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2Plasticizing agent (5) 25 25 25 25 25 25 25 25 25 25 Resin (6) 10 10 1010 10 10 10 10 10 10 Antioxidant (7) 2 2 2 2 2 2 2 2 2 2 Carbon black(8) 5 5 5 5 5 5 5 5 5 5 Stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.52.5 Ex. 17 20 Ex. 18 20 Ex. 19 20 Ex. 20 20 Ex. 23 (Commercial Product)20 Ex. 22 (Commercial Product) 20 Ex. 24 (Commercial Product) 20 Ex. 2620 ZnO (9) 2 2 2 2 2 2 2 2 2 2 Accelerator 1 (10) 1.8 1.8 1.8 1.8 1.81.8 1.8 1.8 1.8 1.8 Sulfur 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2Accelerator 2 (11) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Total PHR221.5 241.5 241.5 241.5 241.5 241.5 241.5 241.5 241.5 221.5 (1) Naturalrubber SIR 10 (Standard Indonesian Rubber) (2) Amorphous Silica (ZEOSIL®1165MP from Rhodia) (3) High-cis BR (BUDENE® 1280 from GoodyearChemical) (4) Silane coupling agent TESPT (Si69® from Evonik Industries)(5) High viscosity naphthenic black oil (NYTEX® 4700 from Nynas AB) (6)Hydrocarbon resin (Escorez™ E5320 from ExxonMobil Chemical Co.) (7)N-(1,3-Dimethylbutyl)-N′-phenyl-p-phenylenediamine (Santoflex^(Ⓡ) 6-PPDfrom Flexsys) (8) Carbon black (Vulcan®3 N330 from Cabot Corp.) (9) Zincoxide in naphthenic oil (AKRO-ZINC® BAR 85 from Akrochem Corp.) (10)N-cyclohexyl-2-benzothiazylsulfenamide (CBS from Kemai Chemical Co.)(11) Diphenyl guanidine (Ekaland DPG from MLPC International (Arkema)

A third set of low filler tread compound formulations are listed belowas tread formulations TT20 to TT27. Control tire tread compound controlswith no Table 1 polymer are tread formulations TT20 and TT27.

Tread Formulations (TT20 to TT27) Ingredient TT20 TT21 TT22 TT23 TT24TT25 TT26 TT27 NR (1) 50 50 50 50 50 50 50 50 Silica (2) 65 65 65 65 6565 65 65 BR (3) 50 50 50 50 50 50 50 50 Coupling agent (4) 5.2 5.2 5.25.2 5.2 5.2 5.2 5.2 Plasticizing agent (5) 15 15 15 15 15 15 15 15 Resin(6) 15 15 15 15 15 15 15 15 Antioxidant (7) 2 2 2 2 2 2 2 2 Carbon black(8) 5 5 5 5 5 5 5 5 Stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Ex. 21(Commerical Product) 20 Ex. 28 20 Ex. 31 20 Ex. 30 20 Ex. 29 20 Ex. 25(Commercial Product) 20 ZnO (9) 2 2 2 2 2 2 2 2 Accelerator 1 (10) 1.81.8 1.8 1.8 1.8 1.8 1.8 1.8 Sulfur 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2Accelerator 2 (11) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 TOTAL PHR 216.50236.50 236.50 236.50 236.50 236.50 236.50 216.50 (1) Natural rubber SIR10 (Standard Indonesian Rubber) (2) Amorphous Silica (ZEOSILⓇ 1165MPfrom Rhodia) (3) High-cis BR (BUDENEⓇ 1280 from Goodyear Chemical) (4)Silane coupling agent TESPT (Si69Ⓡ from Evonik Industries) (5) Sunflowerseed oil (from Spectrum Chemical Mfg. Corp.) (6) Hydrocarbon resin(Escorez™ E5320 from ExxonMobil Chemical Co.) (7)N-(1,3-Dimethylbutyl)-N′-phenyl-p-phenylenediamine (Santoflex^(Ⓡ) 6-PPDfrom Flexsys) (8) Carbon black (VulcanⓇ3 N330 from Cabot Corp.) (9) Zincoxide in naphthenic oil (AKRO-ZINCⓇ BAR 85 from Akrochem Corp.) (10)N-cyclohexyl-2-benzothiazylsulfenamide (CBS from Kemai Chemical Co.)(11) Diphenyl guanidine (Ekaland DPG from MLPC International (Arkema)

Loss Tangent Measurements

Dynamic Mechanical Thermal Analysis (DMTA) test method.

All tread formulations were compression molded and cured into pads.Afterward, a rectangular test specimen (12 mm wide & 30 mm long) wasdied out of the cured pads and mounted in an ARES G2 (AdvancedRheometric Expansion System, TA instruments) for dynamic mechanicaltesting in torsion rectangular geometry. Though the thickness of thetest specimen was around 1.8 mm, the thickness of the specimens variedand was measured manually for each test. A strain sweep at roomtemperature up to 5.5% strains and at 10 Hz was conducted first followedby a temperature sweep at 4% strain and 10 Hz from -26° C. to 100° C. at2° C./min ramp rates. Storage and loss moduli were measured along withthe loss tangent values. For better wet traction, it is preferred tohave higher loss tangent values at a temperatures of 0° C. For betterrolling resistance, the loss tangent is preferred to be lower at atemperature of 60° C. The temperature at which the maximum tan deltaoccurred was recorded as the glass transition temperature, Tg.

The tables below provide the loss tangent measurements and thenormalized loss tangent measurements for the winter tire treadformulations TT1 to TT9, TT10 to TT19 and TT20 to TT27, respectively,using the polymers of Table 1. The tables with the normalized losstangent measurements provide the same measurements but as a percentageof the corresponding control tire tread formulation, TT1 and TT9 for TT2to TT8, TT10 and TT19 for TT11 to TT18 and TT20 and TT27 for TT21 toTT26.

DMTA Tan (delta) Test Results for low filler tire tread formulationsTT1-TT9 Temperature (°C) Controls (TT1 & TT9) avg. TT2 TT3 TT4 TT5 TT6TT7 TT8 0 0.225 0.262 0.276 0.266 0.256 0.303 0.265 0.321 60 0.128 0.1110.111 0.108 0.106 0.077 0.112 0.123 Tan (delta)- normalized to controlsamples Temperature (°C) Controls (TT1 & TT9) avg. TT2 TT3 TT4 TT5 TT6TT7 TT8 0 100 116.5 122.8 118.6 114.1 135.0 117.8 142.8 60 100 86.4 87.084.3 83.2 59.9 87.3 95.9

The addition of the polymer additive compound (Table 1) to the lowfiller winter tread formulation, as compared to the correspondingcontrol, improved wet traction (increased loss tangent at 0° C.) andimproved roll resistance (decreased loss tangent at 60° C.). Improvedwet traction is especially important for winter tread formulations. Inone example, tire tread formulation TT8, comprising the functionalizedpolymer of Example 27 (partially epoxidized EPDM), demonstrated 42%improved wet traction over its control formulation.

DMTA Tan (delta) and Normalized Tan (delta) Test Results for low fillertire tread formulations TT10 to TT19 Tan (delta) Temperature (°C)Controls (TT10 & TT19) avg. TT11 TT12 TT13 TT14 TT15 TT16 TT17 TT18 00.180 0.256 0.261 0.230 0.230 0.244 0.250 0.243 0.245 60 0.087 0.0920.091 0.095 0.090 0.086 0.084 0.089 0.095 Tan (delta)- Normalized tocontrol samples Temperature (°C) Controls (TT10 & TT19) avg. TT11 TT12TT13 TT14 TT15 TT16 TT17 TT18 0 100 141.8 144.8 127.2 127.4 135.1 138.7134.6 135.7 60 100 105.9 104.0 108.4 103.0 98.8 96.1 101.9 109.0

The addition of the polymer/additive compound (Table 1) to the lowfiller tread formulation, as compared to the corresponding control,improved wet traction (increased loss tangent at 0° C.) and/or improvedroll resistance (decreased loss tangent at 60° C.). The examples of thisset of winter tire tread formulations demonstrated over 127% improvedwet traction over its control formulation.

DMTA Test (Tan delta) and Normalized Tan delta Results for low fillertire tread formulations TT20 to TT27 Tan (delta) Temperature (°C)Controls (TT20 & TT27) avg. TT21 TT22 TT23 TT24 TT25 TT26 0 0.176 0.2360.302 0.324 0.209 0.340 0.230 60 0.099 0.098 0.099 0.098 0.093 0.0970.093 Tan (delta)- normalized to control samples Temperature (°C)Controls (TT20 & TT27) avg. TT21 TT22 TT23 TT24 TT25 TT26 0 100 134.2171.5 184.3 118.5 193.3 130.7 60 100 99.1 100.0 99.2 93.3 97.5 93.8

The addition of the polymer/additive compound (Table 1) to the lowfiller winter tread formulation, as compared to the correspondingcontrol, improved wet traction (increased loss tangent at 0° C.) andimproved roll resistance (decreased loss tangent at 60° C.). Theexamples of this set of winter tire tread formulations demonstrated over118% improved wet traction over its control formulation.

Peak Tan Delta temperature (°C) (Tg) for tire tread formulationsTT1-TT19, TT10-TT19 and TT20 to TT27.

Control TT1 TT2 TT3 TT4 TT5 TT6 TT7 TT8 Control TT9 -54 -50 -52 -52 -50-52 -52 -52 -54 Control TT10 TT11 TT12 TT13 TT14 TT15 TT16 TT17 TT18Control TT19 -48 -48 -48 -48 -48 -46 -48 -48 48 -48 Control TT20 TT21TT22 TT23 TT24 TT25 TT26 Control TT27 -52 -52 -52 -52 -52 -50 -50 -52

As shown above, the peak tan delta temperature (°C) or Tg stayed thesame or increased the Tg of the formulation slightly with the additionof the polymer from Table 1 to tire tread formulations TT2-TT8,TT11-TT18 and TT21-TT26. For those formulations where the Tg increased,it is expected that raising the compound glass transition temperature(Tg) would provide better wet traction but, at the same time, increasethe rolling resistance and tread wear. Thus, it is expected that thatraising the compound glass transition temperature (Tg) would providebetter wet traction and increased rolling resistance and tread wear.However, as seen above, the addition of the polymer additive in tiretread formulations TT2 to TT8, TT11 to TT18 and TT21 to TT26 led toimproved results in the form of increased wet traction, decreased rollresistance and decreased tread wear. Improved increased wet traction forwinter tread formulations is a desireable property.

In the specification and in the claims, the terms “including” and“comprising” are open-ended terms and should be interpreted to mean“including, but not limited to”. These terms encompass the morerestrictive terms “consisting essentially of” and “consisting of.”

It must be noted that as used herein and in the appended claims, thesingular forms “a”, “an”, and “the” include plural reference unless thecontext clearly dictates otherwise. As well, the terms “a” (or “an”),“one or more” and “at least one” can be used interchangeably herein. Itis also to be noted that the terms “comprising”, “including”,“characterized by” and “having” can be used interchangeably.

What is claimed is:
 1. An elastomeric composition comprising, per 100parts by weight of rubber (phr): about 30 to about 70 phr ofpolybutadiene having a cis-1,4 linkage content of at least 95%; about 30to 70 phr of natural rubber or polyisoprene; about 20 to 50 phr of aprocessing oil; a curative agent; an antioxidant; about 50 to about 80phr filler; a silane coupling agent; and about 5 to about 30 phr of apolymer selected from the group consisting of ethylene-propylene-dieneterpolymer, butyl rubber, poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer.
 2. Theelastomeric composition of claim 1, wherein the polymer isfunctionalized with an epoxy, thioacetate, mercaptobenzothiazole, amineionomer, phosphine ionomer or citranellol functional group. 3.(canceled)
 4. The elastomeric composition of claim 1, wherein theethylene-propylene-diene terpolymer is epoxidizedethylene-propylene-diene terpolymer.
 5. (canceled)
 6. The elastomericcomposition of claim 1, wherein the ethylene-propylene-diene terpolymercontains from about 1 to 10 wt% ethylidene norbornene based on theterpolymer.
 7. The elastomeric composition of claim 1, wherein theethylene-propylene-diene terpolymer contains from about 5 to 25 wt%ethylene based on the terpolymer.
 8. The elastomeric composition ofclaim 1, wherein the ethylene-propylene-diene terpolymer contains fromabout 65 to 95 wt% propylene based on the terpolymer.
 9. The elastomericcomposition of claim 1, wherein the polymer is halogenated. 10-11.(canceled)
 12. The elastomeric composition of claim 1, wherein the butylrubber is brominated poly(isobutylene-co-isoprene).
 13. The elastomericcomposition of claim 12, wherein the brominatedpoly(isobutylene-co-isoprene) is an amine ionomer derived frombrominated poly(isobutylene-co-isoprene).
 14. (canceled)
 15. Theelastomeric composition of claim 12, wherein the brominatedpoly(isobutylene-co-isoprene) is star-branched brominatedpoly(isobutylene-co-isoprene).
 16. (canceled)
 17. The elastomericcomposition of claim 1, wherein thepoly(isobutylene-co-para-methylstyrene) is brominatedpoly(isobutylene-co-para-methystyrene).
 18. The elastomeric compositionof claim 17, wherein the poly(isobutylene-co-para-methylstyrene)terpolymer is an amine ionomer derived from brominatedpoly(isobutylene-co-para-methylstyrene).
 19. (canceled)
 20. Theelastomeric composition of claim 1, wherein thepoly(isobutylene-co-para-methylstyrene) is a thioacetate functionalizedpoly(isobutylene-co-para-methylstyrene).
 21. The elastomeric compositionof claim 1, wherein the poly(isobutylene-co-para-methylstyrene) is amercaptobenzothiazole functionalizedpoly(isobutylene-co-para-methylstyrene).
 22. The elastomeric compositionof claim 1, wherein the poly(isobutylene-co-para-methylstyrene) is acitronellol functionalized poly(isobutylene-co-para-methylstyrene). 23.The elastomeric composition of claim 1, wherein the polymer selectedfrom the group consisting of ethylene-propylene-diene terpolymer, butylrubber, poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur.
 24. The elastomeric composition of claim 1,wherein the polymer selected from the group consisting ofethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and an activator.
 25. The elastomericcomposition of claim 1, wherein the polymer selected from the groupconsisting of ethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and a silane coupling agent.
 26. Theelastomeric composition of claim 25, wherein the silane coupling agentis selected from the group consisting oftriethoxysilylpropyl)tetrasulphide, bis[3-(diethoxyoctyloxysilyl)propyl]tetrasulfide and bis(triethoxysilylpropyl)tetrasulphide.
 27. (canceled)
 28. The elastomeric composition of claim1, wherein the polymer selected from the group consisting ofethylene-propylene-diene terpolymer, butyl rubber,poly(isobutylene-co-para-methylstyrene) andpoly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymer isfunctionalized with sulfur and a vulcanizing accelerator.
 29. Theelastomeric composition of claim 28, wherein the vulcanizing acceleratoris n-tertiary-butyl-2-benzothiazylsulfenamide. 30-32. (canceled)
 33. Theelastomeric composition of claim 1, further comprising about 1 to 20 phrhydrocarbon resin.
 34. The elastomeric composition of claim 1, whereinthe glass transition temperature (Tg) is from about 20° C. to about -60°C.
 35. (canceled)
 36. The elastomeric composition of claim 1, whereinthe poly(isobutylene-co-para-methylstyrene-co-isoprene) terpolymercontains from 4-8 mol% p-methylstyrene, 0.2-2 mol%isoprene and 90-95mol% isobutylene based on the terpolymer.
 37. A tire tread compositioncomprising the elastomeric composition of claim
 1. 38-39. (canceled)